Application of azine quinone hybrid as negative electrode material and aqueous organic battery

Abstract

The invention discloses an azine quinone hybrid negative electrode material and an aqueous organic battery. The azine-quinone hybrid used as the negative electrode material of the aqueous organic battery has higher discharge capacity compared with an azine material applied to the existing aqueous organic battery, and has longer cycle life compared with a quinone material; the water-based organic battery is formed by taking the azine quinone hybrid as a negative electrode, taking commercial sintered nickel as a positive electrode, taking a KOH solution as an electrolyte and taking polybenzimidazole or PP / PE as a diaphragm, has the advantages of long cycle life, high output voltage and the like, and is wide in raw material source, low in price, high in efficiency and high in reliability. The problems of low energy density and short cycle life of the existing water-based battery can be effectively solved, and the application of the water-based battery in the field of energy storage can be promoted.

Description

Technical Field

[0001] The invention belongs to the technical field of organic batteries, and specifically relates to an application of a quinone hybrid as a negative electrode material and an aqueous organic battery. Background Art

[0002] Lithium-ion batteries have been widely used in portable electronics, electric vehicles, and grid energy storage systems. However, the scarcity of lithium resources, uneven geographical distribution, high cost, and safety risks have severely limited their application in large-scale energy storage systems. Among various new rechargeable batteries, aqueous batteries have attracted widespread attention in recent years due to their inherent safety, low cost, easy preparation, and environmental friendliness.

[0003] Traditional aqueous batteries include nickel-metal hydride batteries, lead-acid batteries, nickel-chromium batteries, etc. Electrode materials play a vital role in these batteries because they will determine the energy density and cycle performance of the battery. So far, various inorganic electrode materials in aqueous batteries have been widely studied, but factors such as their dissolution and structural changes have led to poor cycle performance of most materials. Compared with inorganic materials, organic materials rearrange chemical bonds during the redox process, which to a certain extent avoids structural collapse. In addition, unlike the rigid structure of organic materials, organic molecular structures show great flexibility, which promotes the carrying capacity of carriers of different valence states. In recent years, more and more researchers have proposed many organic materials (such as azine materials, quinone materials, conductive polymers, etc.) for aqueous zinc batteries, aqueous lithium batteries, aqueous aluminum batteries, etc., considering the structural diversity of organic materials and the advantages of resource sustainability.

[0004] Nevertheless, the development of aqueous batteries is still in its early stages, and there are still some problems to be solved: 1) The practical application of most organic materials is limited by expensive raw materials, complex synthesis and low yield; 2) In most cases, high energy density and good cycle performance cannot be obtained at the same time. Therefore, in order to promote the practical application of aqueous organic batteries, it is still necessary to explore organic materials that are easy to synthesize, have high energy density and are durable. Summary of the invention

[0005] The purpose of this section is to summarize some aspects of embodiments of the present invention and briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section and the specification abstract and the invention title of this application to avoid blurring the purpose of this section, the specification abstract and the invention title, and such simplifications or omissions cannot be used to limit the scope of the present invention.

[0006] In view of the above problems and / or the problems existing in the prior art, the present invention is proposed.

[0007] Therefore, the purpose of the present invention is to overcome the deficiencies in the prior art and provide an application of a quinone hybrid as a negative electrode material. The structural formula of the quinone hybrid is shown in Formula I;

[0008]

[0009] As a preferred embodiment of the application of the azinequinone hybrid of the present invention as a negative electrode material, the preparation method of the azinequinone hybrid comprises:

[0010] 2,5-dihydroxy-1,4-benzoquinone and o-phenylenediamine are uniformly mixed in a molar ratio of 1:4 to obtain a mixture;

[0011] The mixture is heated at 15-200°C for 4-6 hours under N2 atmosphere;

[0012] After cooling to room temperature, the product was washed several times with deionized water and acetone, respectively, and dried under vacuum at 80°C for 18 to 24 h to obtain the intermediate product 5,12-dihydroquinol[2,3-b]phenazine (DHTAP);

[0013] DHTAP was added to a sulfuric acid solution with a concentration of 3-5 mol / L, K2CrO7 was slowly added, the molar ratio of DHTAP to K2CrO7 was 1:4, stirred at 80°C for 4 hours, and cooled in ice water to obtain the final product;

[0014] The final product was washed several times with deionized water and acetone, filtered, and vacuum dried to obtain a quinone hybrid, which was used as a negative electrode material for aqueous organic batteries.

[0015] As a preferred embodiment of the application of the azinequinone hybrid of the present invention as a negative electrode material, the preparation method of the negative electrode material comprises:

[0016] mixing the quinone hybrid with a conductive agent and a binder;

[0017] Isopropanol is added and ground evenly, vacuum dried, rolled, cut into thin slices and pressed onto a foamed nickel current collector, and then vacuum dried to obtain an organic negative electrode material.

[0018] As a preferred solution for using the quinone hybrid of the present invention as a negative electrode material, the mass ratio of the quinone hybrid, the conductive agent and the binder is 5-7:3-5:1.

[0019] As a preferred solution for using the azinequinone hybrid of the present invention as a negative electrode material, the conductive agent is Ketjen black, carbon nanotubes, graphene oxide, conductive carbon black, and activated carbon.

[0020] As a preferred solution for using the azinequinone hybrid as a negative electrode material according to the present invention, the binder is polytetrafluoroethylene, polyvinylidene fluoride, or polyethylene dioxythiophene.

[0021] As a preferred solution for using the azinequinone hybrid of the present invention as a negative electrode material, the vacuum drying temperature is 40 to 80° C. and the drying time is 20 to 60 minutes.

[0022] The purpose of the present invention is to overcome the deficiencies in the prior art and provide an aqueous organic battery, characterized in that the negative electrode material is used as the negative electrode, commercial sintered nickel is used as the positive electrode, the electrolyte is a KOH solution, and a diaphragm is added to construct an aqueous organic battery.

[0023] As a preferred embodiment of the aqueous organic battery of the present invention, the separator comprises polybenzimidazole and PP / PE.

[0024] As a preferred embodiment of the aqueous organic battery of the present invention, the cycle life of the aqueous organic battery is more than 5000 times.

[0025] Beneficial effects of the present invention:

[0026] (1) The negative electrode used in the present invention is a quinone hybrid (TAPQ), which has a higher discharge capacity than the quinone materials used in existing aqueous organic batteries, and has a higher cycle life than the quinone materials;

[0027] (2) Aqueous organic batteries composed of TAPQ organic negative electrode and commercial sintered nickel positive electrode have the advantages of long cycle life and high output voltage. In addition, the raw materials are widely available and inexpensive. They can effectively solve the problems of low energy density and short cycle life of existing aqueous batteries, and help promote the application of aqueous batteries in large-scale energy storage. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following briefly introduces the drawings required for describing the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without creative labor. Among them:

[0029] Figure 1 is the structural formula of TAPQ in Example 1.

[0030] Figure 2 This is the NMR spectrum of TAPQ in Example 1.

[0031] Figure 3This is the cyclic voltammetry curve of TAPQ at 5 mV / s in the three-electrode system in Example 1.

[0032] Figure 4 This is a cycle curve of the aqueous organic battery in Example 1 at 0.1 A / g.

[0033] Figure 5 This is a cycle curve of the aqueous organic battery in Example 2 at 0.1 A / g. DETAILED DESCRIPTION

[0034] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, the specific implementation methods of the present invention are described in detail below in conjunction with the embodiments of the specification.

[0035] In the following description, many specific details are set forth to facilitate a full understanding of the present invention, but the present invention may also be implemented in other ways different from those described herein, and those skilled in the art may make similar generalizations without violating the connotation of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed below.

[0036] Secondly, the term "one embodiment" or "embodiment" as used herein refers to a specific feature, structure, or characteristic that may be included in at least one implementation of the present invention. The term "in one embodiment" that appears in different places in this specification does not necessarily refer to the same embodiment, nor does it refer to a separate or selective embodiment that is mutually exclusive with other embodiments.

[0037] The raw materials used in the present invention are all commercially available in the art unless otherwise specified. The PP / PE diaphragm was purchased from Laizhou Lianyou Jinhao New Materials Co., Ltd., with a thickness of 0.19±0.02mm and a surface density of 72.0±6.0g / m 3 ; PBI diaphragm thickness is 25μm; sintered nickel is purchased from Haisida Group, with a surface density of 27mAh / cm 2 ; o-phenylenediamine was purchased from Sinopharm Group with a purity of ≥98.5%; 2,5-dihydroxy-1,4-benzoquinone was purchased from Aladdin Company with a purity of ≥98%.

[0038] Example 1

[0039] This embodiment provides a method for preparing TAPQ, and the specific steps are:

[0040] Take 1.4 g (10 mmol) of 2,5-dihydroxy-1,4-benzoquinone and 4.33 g (40 mmol) of o-phenylenediamine and mix them evenly in a mortar;

[0041] The mixture was placed in a tube furnace and heated at 180 °C for 5 h under N2 atmosphere;

[0042] After cooling to room temperature, the product was washed several times with deionized water and acetone, respectively, and dried in a vacuum drying oven at 80°C for 18 h to obtain the intermediate product DHTAP;

[0043] Take 25 ml (98% H2SO4) and add it to 100 ml deionized water, then add 2 g (7 mmol) DHTAP, slowly add 8.24 g K2CrO7 (28 mmol), stir at 80 ° C for 4 hours, and then pour it into 200 ml ice water;

[0044] The final product was washed several times with deionized water and acetone, filtered, and the filter cake was dried in a vacuum oven at 80° C. for 18 h to obtain TAPQ.

[0045] The synthesis reaction of TAPQ is shown in Formula II:

[0046]

[0047] This embodiment provides a method for preparing a negative electrode material, specifically:

[0048] Mix 120 mg TAPQ, 60 mg Ketjen black (KB), and 20 mg polytetrafluoroethylene (PTFE) in a mass ratio of 6:3:1;

[0049] Add appropriate amount of isopropanol, grind in agate mortar for 60 minutes, place in 40℃ vacuum drying oven for 60 minutes, then mix the materials into plasticine and press into thin sheets, cut into 1*1cm pieces with scissors. 2 A small piece of electrode material is pressed onto nickel foam at a pressure of 10 MPa to obtain an organic negative electrode material.

[0050] The TAPQ organic negative electrode material was subjected to a cyclic voltammetry test under a three-electrode system. The specific process is as follows: the electrolyte is 50 mL of 6M KOH solution, the TAPQ / KB electrode is the working electrode, Hg / HgO is the reference electrode, and the graphite rod is the counter electrode. The three-electrode system is assembled and a cyclic voltammetry test is performed to evaluate the TAPQ redox peak position. The Nova electrochemical workstation is used, the voltage range is 0 to -1.1V, discharge first and then charge, and the scan rate is 5mV / s.

[0051] This embodiment provides an aqueous organic battery, specifically: TAPQ organic electrode is used as the negative electrode, 6MKOH solution is used as the electrolyte, PBI is used as the separator, and sintered nickel with a diameter of 10 mm is used as the positive electrode, which is assembled into a CR2032 button battery.

[0052] The cycle performance of aqueous organic batteries was tested using a new well battery tester. After the battery was assembled, it was left for 12 hours before the charge and discharge test, first charging and then discharging, with a voltage range of 1.5 to 0.5 V and a current density of 0.1 Ag. -1, the current size is set according to the mass of TAPQ in the negative electrode, and the specific capacity of the aqueous organic battery is calculated based on the mass of TAPQ in the negative electrode.

[0053] Figure 1 is the structural formula of TAPQ of this embodiment.

[0054] Figure 2 : is the hydrogen nuclear magnetic resonance spectrum of TAPQ in this example, wherein the peaks at 8.2 and 8.48 ppm with equal integrated areas indicate two hydrogen atoms of TAPQ.

[0055] Figure 3 This is the cyclic voltammetry curve of TAPQ at 5mV / s in a three-electrode system. During the discharge process, three peaks corresponding to the reduction reaction appear: -0.98V, -0.76V, and -0.20V. During the charge process, three peaks corresponding to the oxidation reaction appear: -0.84V, -0.62V, and -0.14V, indicating that the redox reaction of TAPQ is carried out step by step, with high reversibility and low potential, making it suitable for use as a negative electrode.

[0056] The aqueous organic battery of this embodiment was tested at 0.1A g -1 The charge and discharge curves of the 1st, 5th, 10th, 15th, 20th, 25th, 30th, 35th and 40th cycles are shown below. Figure 4 As shown. At 0.1A g -1 The reversible capacities under -1 , 279.34mAh g -1 、250.93mAh g -1 , 226.43mAh g -1 , 210.32mAh g -1 , 198.46mAh g -1 , 192.19mAh g -1 , 185.98mAh g -1 , 181.98mAh g -1 .

[0057] Example 2

[0058] The difference between this embodiment and embodiment 1 is that PP / PE is selected as the separator, and the other steps are the same as those in embodiment 1, and a CR2032 button battery is assembled.

[0059] The aqueous organic battery of this embodiment was tested at 0.1A g -1 The charge and discharge curves of the 1st, 5th, 10th, 15th, 20th, 25th, 30th, 35th and 40th cycles are shown below. Figure 5 As shown. At 0.1A g-1 The reversible capacities under -1 , 229.63mAh g -1 , 206.25mAh g -1 , 185.48mAh g -1 、172.06mAh g -1 、162.5mAh g -1 , 152.13mAh g -1 , 144.24mAh g -1 、136.2mAh g -1 .

[0060] Since TAPQ dissolves in alkaline electrolyte, when using ordinary PP / PE separators, the dissolved TAPQ penetrates the separator and enters the electrode, causing a micro short circuit, resulting in poor discharge capacity and cycle stability. In Example 1, a PBI separator is used, which can only allow ions to pass through, but the dissolved TAPQ cannot penetrate. Therefore, the discharge capacity and cycle stability of TAPQ in Example 1 are better than those in Example 2.

[0061] Example 3

[0062] The difference between this embodiment and embodiment 1 is that TAPQ:KB:PTFE=7:3:1, and the other steps are the same as those in embodiment 1, and a CR2032 button battery is assembled.

[0063] The aqueous organic battery of this embodiment was tested at 0.1A g -1 The charge-discharge curves of the 1st, 5th, 10th, 15th, 20th, 25th, 30th, 35th and 40th cycles were taken. The results showed that the reversible capacity at 0.1A g-1 reached 210.63 mAh g -1 , 154.45mAh g -1 , 123.66mAh g -1 , 104.17mAh g -1 , 91.41mAh g -1 , 81.41mAh g -1 , 81.49mAh g -1 、73.68mAh g -1 、68.18mAh g -1 .

[0064] Since TAPQ has poor conductivity, a specific proportion of conductive agent needs to be added to ensure electron transmission during charge and discharge when preparing electrode materials. In this embodiment, since the proportion of conductive carbon is reduced, its discharge capacity and cycle performance are worse than those of Example 1.

[0065] Comparative Example 1

[0066] The difference between this comparative example and Example 1 is that no separator is added to the aqueous organic battery, and the battery short-circuit occurs, so a separator must be added to the battery.

[0067] Comparative Example 2

[0068] The difference between this comparative example and Example 1 is that sintered nickel is used as the negative electrode and TAPQ is used as the positive electrode, the battery voltage is negative, and charging and discharging cannot be performed.

[0069] Comparative Example 3

[0070] The discharge capacity and cycle life of the TAPQ organic negative electrode of Example 1 are compared with those of the azine-based material and quinone-based material in the prior art, as shown in Table 1.

[0071] Table 1 Comparison of properties of azine and quinone materials

[0072] Material As positive / negative electrode Discharge capacity Cycle life Phenazine negative electrode 282.3mAh / g 5000 Diaminophenazine negative electrode 236.5mAh / g 1000 9,10-Propiophenylone positive electrode 150mAh / g 3000 TAPQ negative electrode 313.9mAh / g 5000

[0073] As can be seen from Table 1, since TAPQ has multiple redox centers, the discharge capacity of TAPQ organic negative electrode is significantly higher than that of other materials.

[0074] Comparative Example 4

[0075] The performance of the aqueous organic battery of Example 1 of the present invention and the aqueous battery in the prior art are compared, as shown in Table 2.

[0076] Table 2 Comparison of performance of different aqueous batteries

[0077] Cathode Materials Anode Materials Diaphragm Electrolyte solution Cycle life Output voltage <![CDATA[Ni(OH)2]]> Hydrogen Storage Alloys Polypropylene KOH 500-1000 1.2V <![CDATA[PbO2]]> Pb Microporous rubber sulfuric acid 500-1000 2V <![CDATA[Ni(OH)2]]> Cadmium Metal Polyamide NaOH More than 500 times 1.2V <![CDATA[Ni(OH)2]]> iron Polypropylene NaOH More than 500 times 1.2V <![CDATA[Ni(OH)2]]> TAPQ PBI diaphragm KOH More than 5000 times 1V

[0078] As can be seen from Table 2, in existing aqueous batteries, the positive or negative electrode materials of the battery are all inorganic materials, such as metal cadmium and lead as the negative electrode. These materials are not only toxic, but also have the hidden danger of resource shortage. In contrast, the negative electrode of the aqueous organic battery of the present invention uses TAPQ, which has simple material synthesis and abundant raw materials, low cost, and a cycle life of more than 5,000 times, which is much higher than the aqueous batteries currently used commercially.

[0079] In summary, the negative electrode material TAPQ used in the present invention has a higher discharge capacity than the azine materials used in existing aqueous organic batteries, and has a higher cycle life than the quinone materials; the aqueous organic battery composed of TAPQ organic negative electrode and commercial sintered nickel positive electrode has the advantages of long cycle life and high output voltage, and the raw materials are widely available and inexpensive, which can effectively solve the problems of low energy density and short cycle life of existing aqueous batteries.

[0080] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention rather than to limit it. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present invention may be modified or replaced by equivalents without departing from the spirit and scope of the technical solutions of the present invention, which should all be included in the scope of the claims of the present invention.

Claims

1. An application of a quinone hybrid as a negative electrode material, characterized in that: The structural formula of the quinone hybrid is shown in Formula I; 2. The use of the quinone hybrid as claimed in claim 1 as a negative electrode material, characterized in that: The preparation method of the azinequinone hybrid comprises: 2,5-dihydroxy-1,4-benzoquinone and o-phenylenediamine are uniformly mixed in a molar ratio of 1:4 to obtain a mixture; The mixture was heated at 150-200°C for 4-6 hours under N2 atmosphere; After cooling to room temperature, the product was washed several times with deionized water and acetone, respectively, and dried under vacuum at 80°C for 18-24h to obtain the intermediate product DHTAP; DHTAP was added to a sulfuric acid solution with a concentration of 3-5 mol / L, K2CrO7 was slowly added, the molar ratio of DHTAP to K2CrO7 was 1:4, stirred at 80°C for 4 hours, and cooled in ice water to obtain the final product; The final product was washed several times with deionized water and acetone, filtered, and vacuum dried to obtain a quinone hybrid, which was used as a negative electrode material for aqueous organic batteries.

3. The use of the quinone hybrid as claimed in claim 1 as a negative electrode material, characterized in that: The method for preparing the negative electrode material comprises: mixing the quinone hybrid with a conductive agent and a binder; Isopropanol is added and ground evenly, vacuum dried, rolled, cut into thin slices and pressed onto a foamed nickel current collector, and vacuum dried to obtain a negative electrode material.

4. The use of the quinone hybrid as a negative electrode material according to claim 3, characterized in that: The mass ratio of the quinone hybrid, the conductive agent and the binder is 5-7:3-5:

1.

5. The use of the quinone hybrid as a negative electrode material according to claim 3, characterized in that: The conductive agent includes Ketjen black, carbon nanotubes, graphene oxide, conductive carbon black and activated carbon.

6. The use of the quinone hybrid as a negative electrode material according to claim 3, characterized in that: The binder includes polytetrafluoroethylene, polyvinylidene fluoride, and polyethylene dioxythiophene.

7. The use of the quinone hybrid as a negative electrode material according to claim 3, characterized in that: The vacuum drying temperature is 40-80° C. and the time is 20-60 minutes.

8. An aqueous organic battery, characterized in that: The negative electrode material according to any one of claims 1 to 7 is used as the negative electrode, commercial sintered nickel is used as the positive electrode, the electrolyte is a KOH solution, and a diaphragm is added to construct an aqueous organic battery.

9. The aqueous organic battery according to claim 8, wherein: The separator includes polybenzimidazole and PP / PE.

10. The aqueous organic battery according to claim 8, wherein: The aqueous organic battery has a cycle life of more than 5,000 times.

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