An all-organic aqueous zinc ion battery positive electrode material and a preparation method and application thereof

Abstract

The application discloses a kind of all-organic aqueous zinc ion battery positive electrode materials and preparation method and application, belong to new energy materials and battery technical field, and positive electrode material is nitrogen heterocyclic organic 5,5,12,12'-tetrahydro-2,2'-bi quinoxaline [2,3-b] quinoxaline, negative electrode material is imine and carbonyl organic matter.Nitrogen heterocyclic organic positive electrode loses electron and is oxidized in charging process, and imine and carbonyl organic negative electrode obtains electron and is reduced, so stable charge-discharge cycle can be carried out.The application uses the above-mentioned one all-organic aqueous zinc ion battery positive electrode material and preparation method and application, using structure adjustable and element rich organic positive electrode, relatively stable imine and carbonyl organic negative electrode, environment-friendly and safe water-based electrolyte, can realize the stable charge-discharge of all-organic aqueous zinc ion battery.

Description

Technical Field

[0001] This invention relates to the field of new energy materials and battery technology, and in particular to an all-organic aqueous zinc-ion battery cathode material, its preparation method, and its application. Background Technology

[0002] While state-of-the-art lithium-ion batteries dominate the portable electronics and electric vehicle markets, safety and high cost issues limit their widespread adoption. In contrast, aqueous zinc-ion batteries (ZIBs) boast an exceptionally high theoretical capacity (820 mAh g / g). -1 Its good compatibility with aqueous electrolytes, abundant natural resources, and low toxicity have attracted widespread attention.

[0003] Currently, inorganic cathodes such as manganese oxides, vanadium oxides, and Prussian blue analogues are commonly used in zinc oxides (ZIBs). However, the development of these materials has been severely hampered by limited mineral resources and serious environmental pollution problems. In recent years, organic electrode materials have become attractive cathode candidates due to their inherent advantages of structural diversity and sustainability. Existing organic cathode materials have low operating voltages, which significantly limits their application potential. Therefore, designing a high-voltage organic cathode material has become a research hotspot.

[0004] A key, often overlooked, problem in zinc-organic batteries is the low zinc utilization rate. Dendrite growth and side reactions in aqueous electrolytes lead to poor coulombic efficiency of the zinc anode, making it unsuitable for practical applications. Using organic anodes can mitigate these issues.

[0005] All-organic aqueous batteries, as a new type of rechargeable battery, combine the advantages of a wide variety of organic compounds and easy structural adjustment, with the safety, environmental friendliness, and low cost of aqueous electrolytes, and have great potential in the field of energy storage applications. Summary of the Invention

[0006] The purpose of this invention is to provide a fully organic aqueous zinc-ion battery cathode material, its preparation method, and its application. It employs an organic cathode with tunable structure and abundant elements, relatively stable imine and carbonyl organic anodes, and an environmentally friendly and safe water-based electrolyte, which can achieve stable charging and discharging of the fully organic aqueous zinc-ion battery.

[0007] To achieve the above objectives, this invention provides an all-organic aqueous zinc-ion battery cathode material, wherein the cathode material is 5,5,12,12'-tetrahydro-2,2'-biquinoxalino[2,3-b]quinoxalino, and its structural formula is shown in Formula 1:

[0008] Formula 1:

[0009] This invention provides a method for preparing an all-organic aqueous zinc-ion battery cathode material, comprising the following steps:

[0010] S1. Add the first reactant and the second reactant to the container for pretreatment;

[0011] S2. The product obtained in S1 is processed again, and the reaction is cooled to room temperature after completion.

[0012] S3. After processing the product obtained in S2, wash and vacuum dry it to obtain the cathode material.

[0013] Preferably, the specific operation is as follows:

[0014] S1. Add the first reactant and the second reactant to a three-necked flask, add N,N-dimethylformamide, and obtain a mixed solution;

[0015] S2. Heat the mixed solution under reflux, and after the reaction is complete, cool it to room temperature to obtain product one;

[0016] S3. The product is vacuum filtered, washed alternately with N,N-dimethylformamide and water, and then dried under vacuum to obtain the positive electrode material.

[0017] Preferably, in S1, the amount of the first reactant and N,N-dimethylformamide is such that each mmol of the first reactant is dissolved in 7-8 mL of N,N-dimethylformamide.

[0018] Preferably, the specific operation is as follows:

[0019] S1. Weigh the first reactant and the second reactant, mix them, and grind them to obtain a mixture;

[0020] S2. The mixture is heated to react, and after the reaction is complete, it is cooled to room temperature to obtain product two;

[0021] S3. The product is dispersed in water, washed, and vacuum dried to obtain the cathode material.

[0022] Preferably, the first reactant is a compound of the quinoxaline class having a dichloro structure, and is one or more of 2,3-dichloroquinoxaline, 6-bromo-2,3-dichloro-6-methylquinoxaline, 2,3-dichloro-6,7-difluoroquinoxaline, 2,3-dichloro-6-methoxyquinoxaline, 2,3-dichloro-6,7-dinitroquinoxaline, 2,3-dichloro-6,7-dimethylquinoxaline, and 2,3-dichloro-6,7-dimethoxyquinoxaline;

[0023] The second reactant is a compound having an o-aniline structure, and is one or more of 3,3-diaminobiphenyldiamine, 4,5-difluoro-1,2-phenylenediamine, 4-methoxy-o-phenylenediamine, 4-nitro-o-phenylenediamine, 4-bromo-1,2-phenylenediamine, and 4-fluoro-1,2-phenylenediamine.

[0024] Preferably, in S1, the molar ratio of the first reactant to the second reactant is 1:(1-1.2);

[0025] In S2, the heating temperature is 120-180℃, and the heating time is 5-10h;

[0026] In S3, the number of washing cycles is 3-5, the drying temperature is 80-100℃, and the drying time is 10-12 hours.

[0027] This invention provides an application of an all-organic aqueous zinc-ion battery cathode material, which is applied to an all-organic aqueous zinc-ion battery, comprising an organic cathode, an organic anode, and an aqueous electrolyte.

[0028] Preferably, it includes the following steps:

[0029] A. Grind the positive electrode material and negative electrode material with Ketjen black in a mortar. Then, add N-methylpyrrolidone solution containing 2% polytetrafluoroethylene binder. The mass ratio of the positive electrode material or negative electrode material to Ketjen black and polytetrafluoroethylene is (6-7):3:1. After mixing evenly, coat the mixture onto a stainless steel mesh current collector and dry it in a vacuum drying oven at 70-90℃ for 10-14 hours. Then cut it into 10mm diameter round pieces to obtain organic positive electrode or organic negative electrode.

[0030] B. Separate the organic positive electrode and the organic negative electrode with a glass fiber diaphragm, and inject water-based electrolyte;

[0031] The water-based electrolyte is one or more of zinc trifluoromethanesulfonate, zinc sulfate, zinc acetate, zinc chloride, and zinc perchlorate dissolved in water.

[0032] Preferably, in A, the negative electrode material is an imine-based organic compound, specifically one of dipyridophenazine or dipyridoquinoxaline, with the structural formulas shown in Formulas 2 and 3.

[0033] Formula 2: Dipyridylphenazine;

[0034] Formula 3: Dipyridoquinoxaline;

[0035] Alternatively, the negative electrode material may be a carbonyl organic compound, specifically one of 1,4,5,8-naphthalenetetracarboxylic anhydride or 3,4,9,10-tetracarboxylic anhydride, with the structural formulas shown in Formulas 4 and 5.

[0036] Formula 4: 1,4,5,8-Naphthalenetetracarboxylic anhydride;

[0037] Formula 5: 3,4,9,10-Tetracarboxylic anhydride.

[0038] Therefore, the present invention, employing the above-mentioned all-organic aqueous zinc-ion battery cathode material, its preparation method, and its application, has the following beneficial effects:

[0039] (1) Using nitrogen heterocyclic organic compounds as positive electrode materials, the structure is tunable and rich in elements, and has a high working voltage;

[0040] (2) Using imine and carbonyl organic compounds as negative electrode materials is relatively stable and can achieve stable charging and discharging of all-organic aqueous zinc-ion batteries.

[0041] (3) The water-based electrolyte used is environmentally friendly and safe.

[0042] The technical solution of the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. Attached Figure Description

[0043] Figure 1 This is the FT-IR spectrum of the cathode material of the all-organic aqueous zinc-ion battery of the present invention, its preparation method and application example 1;

[0044] Figure 2 This is a CV diagram of an all-organic aqueous zinc-ion battery cathode material, its preparation method, and an application example of the all-organic aqueous zinc-ion battery according to the present invention.

[0045] Figure 3 This is a rate performance diagram of an all-organic aqueous zinc-ion battery, which is a cathode material for an all-organic aqueous zinc-ion battery according to the present invention, its preparation method, and an application example 1.

[0046] Figure 4 This is a cycle performance diagram of an all-organic aqueous zinc-ion battery cathode material, its preparation method, and an application example of the present invention.

[0047] Figure 5 This is a charge-discharge curve of an all-organic aqueous zinc-ion battery cathode material, its preparation method, and application example two of the present invention.

[0048] Figure 6This is a cycle performance diagram of an all-organic aqueous zinc-ion battery cathode material, its preparation method, and application example three of the present invention.

[0049] Figure 7 This is a charge-discharge curve of an all-organic aqueous zinc-ion battery cathode material, its preparation method, and application example four of the present invention. Detailed Implementation

[0050] The technical solution of the present invention will be further described below with reference to the accompanying drawings and embodiments.

[0051] Unless otherwise defined, the technical or scientific terms used in this invention shall have the ordinary meaning as understood by one of ordinary skill in the art to which this invention pertains.

[0052] Example 1

[0053] A fully organic aqueous zinc-ion battery cathode material, wherein the cathode material is 5,5,12,12'-tetrahydro-2,2'-biquinoxalino[2,3-b]quinoxalino, and its structural formula is shown in Formula 1:

[0054] Formula 1:

[0055] A method for preparing an all-organic aqueous zinc-ion battery cathode material includes the following steps:

[0056] S1. Add 0.4 g of 2,3-dichloroquinoxaline and 0.25 g of 3,3-diaminobiphenyldiamine to a three-necked flask, and add 7 mL of N,N-dimethylformamide to obtain a mixed solution.

[0057] S2. The mixed solution was heated under reflux at 120°C for 5 hours. After the reaction was completed, it was cooled to room temperature to obtain product one.

[0058] S3. The product is vacuum filtered, washed three times with N,N-dimethylformamide and water, and then placed in a vacuum drying oven and dried at 80°C for 12 hours to obtain the positive electrode material.

[0059] The prepared cathode material is applied to an all-organic aqueous zinc-ion battery, which includes an organic cathode, an organic anode, and an aqueous electrolyte. The specific steps include:

[0060] A. Grind 0.06g of 5,5,12,12'-tetrahydro-2,2'-biquinoxalo[2,3-b]quinoxaloline and 0.03g of Ketjen Black conductive agent in a mortar until fully mixed. Then, add 0.5g of NMP (N-methylpyrrolidone) solution containing 2% polytetrafluoroethylene binder, mix thoroughly, and coat the mixture onto a stainless steel mesh current collector. Place the mixture in a vacuum drying oven and dry at 80℃ for 12 hours. Then, cut it into 10mm diameter discs to obtain the organic positive electrode.

[0061] B. Grind 0.06g of dipyridophenezine and 0.03g of Ketjen Black conductive agent in a mortar until fully mixed. Then add 0.5g of NMP (N-methylpyrrolidone) solution containing 2% polytetrafluoroethylene binder, mix well, and apply to a stainless steel mesh current collector. Place in a vacuum drying oven and dry at 80℃ for 12h. Then cut into 10mm diameter discs to obtain the organic negative electrode.

[0062] C. Separate the organic positive electrode and the organic negative electrode with a glass fiber diaphragm, and inject 1 mol / L Zn(OTF)2 electrolyte.

[0063] Example 2

[0064] Unlike Example 1, in Example C, the water-based electrolyte is a 1 mol / L ZnSO4 electrolyte.

[0065] Example 3

[0066] Unlike Example 1, in C, the water-based electrolyte is a 1 mol / L Zn(AC)2 electrolyte.

[0067] Example 4

[0068] Unlike Example 1, in Example B, the negative electrode material is 0.06g of dipyridoquinoxaline.

[0069] Test 1

[0070] Figure 1 This is the FT-IR spectrum of the cathode material prepared in Example 1, at 3433 cm⁻¹. -1 and 533cm -1 The peaks at the positions correspond to the stretching and bending vibrations of -NH-, respectively, indicating that the compound was successfully synthesized.

[0071] Test 2

[0072] Figure 2 The image shows the CV curve of the all-organic aqueous zinc-ion battery prepared in Example 1 at a scan rate of 0.2 mV / s. The results show that both the organic positive electrode and the organic negative electrode exhibit good redox reversibility, and the redox potentials are all within the electrochemical window of the electrolyte. Therefore, the all-organic aqueous zinc-ion battery can work normally.

[0073] Test 3

[0074] Figure 3 The graph shows the rate performance of the all-organic aqueous zinc-ion battery prepared in Example 1. As can be seen from the graph, the battery can return to its initial state after passing through multiple current cycles from a small current, indicating that it has good rate performance.

[0075] Test 4

[0076] Figure 4 The graph shows the cycle performance of the all-organic aqueous zinc-ion battery prepared in Example 1, indicating that the battery has good cycle stability.

[0077] Test 5

[0078] Figure 5 The graph shows a partial charge-discharge curve of the all-organic aqueous zinc-ion battery prepared in Example 2. It can be observed that the coulombic efficiency gradually increases, indicating that the all-organic aqueous zinc-ion battery requires an activation process to improve its charge-discharge efficiency.

[0079] Test 6

[0080] Figure 6 The graph shows the cycle performance of the all-organic aqueous zinc-ion battery prepared in Example 3, indicating that the all-organic aqueous zinc-ion battery has good cycle performance.

[0081] Test 7

[0082] Figure 7 This is the charge-discharge curve of the first 5 cycles of the all-organic aqueous zinc-ion battery prepared in Example 4. It can be observed that the median voltage is approximately 0.40V, and the battery exhibits relatively stable cycle performance. Based on the active mass of the cathode material, this battery achieves a high efficiency of 0.05A g / L. -1 At this current density, the specific capacity during the first charge cycle is 247.385mAh g. -1 The discharge specific capacity is 123.997 mAh g. -1 .

[0083] Therefore, the present invention adopts the above-mentioned all-organic aqueous zinc-ion battery cathode material, its preparation method and application, and uses an organic cathode with tunable structure and abundant elements, a relatively stable imine and carbonyl organic anode, and an environmentally friendly and safe water-based electrolyte, which can achieve stable charging and discharging of the all-organic aqueous zinc-ion battery.

[0084] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit them. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can still be made to the technical solutions of the present invention, and these modifications or equivalent substitutions cannot cause the modified technical solutions to deviate from the spirit and scope of the technical solutions of the present invention.

Claims

1. An application of an all-organic aqueous zinc-ion battery cathode material, characterized in that, The positive electrode material of the all-organic aqueous zinc-ion battery is applied to the all-organic aqueous zinc-ion battery, which includes an organic positive electrode, an organic negative electrode, and a water-based electrolyte. The structural formula of the positive electrode material for an all-organic aqueous zinc-ion battery is shown in Formula 1: Formula 1:

2. The application of the all-organic aqueous zinc-ion battery cathode material according to claim 1, characterized in that, Includes the following steps: A. Grind the positive electrode material and negative electrode material with Ketjen black in a mortar. Then, add an N-methylpyrrolidone solution containing 2% polytetrafluoroethylene. The mass ratio of the positive electrode material or negative electrode material to Ketjen black and polytetrafluoroethylene is (6-7):3:

1. After mixing evenly, coat the mixture onto a stainless steel mesh current collector and dry it in a vacuum drying oven at 70-90℃ for 10-14 hours. Then cut it into 10mm diameter discs to obtain organic positive electrode or organic negative electrode. B. Separate the organic positive electrode and the organic negative electrode with a glass fiber diaphragm, and inject water-based electrolyte; The water-based electrolyte is one or more of zinc trifluoromethanesulfonate, zinc sulfate, zinc acetate, zinc chloride, and zinc perchlorate dissolved in water.

3. The application according to claim 2, characterized in that, In A, the negative electrode material is one of dipyridophenazine or dipyridoquinoxaline, and its structural formula is shown in Formula 2 and Formula 3: Formula 2: Dipyridylphenazine; Formula 3: Dipyridoquinoxaline; Alternatively, the negative electrode material may be one of 1,4,5,8-naphthalenetetracarboxylic anhydride or 3,4,9,10-tetracarboxylic anhydride, with the structural formulas shown in Formulas 4 and 5: Formula 4: 1,4,5,8-Naphthalenetetracarboxylic anhydride; Formula 5: 3,4,9,10-Tetracarboxylic anhydride.

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