Quinones derivative electrode based on C+N bond number regulation and application thereof

Abstract

The invention belongs to the technical field of quinone derivative electrode materials, and particularly discloses a quinone derivative electrode based on C = N bond number regulation and application thereof, the structure of the quinone derivative electrode comprises one of the following structural general formulas: in the general formula 1 and the general formula 2, an Ar group comprises aromatic hydrocarbon and heterocyclic aromatic hydrocarbon, and an Arl group and an Ar2 group are the same or different; the R group comprises H, halogen, alkyl, halogenated alkyl, amino, hydroxyl, alkoxy, ester group, acyl, cyano, aromatic hydrocarbon and heterocyclic aromatic hydrocarbon, and the R1 group and the R2 group are the same or different. According to the quinone derivative electrode based on C = N bond number regulation and the application of the quinone derivative electrode, the quinone derivative electrode stores energy by means of hydrogen bond formation and fracture of ammonium ions and C = O in the charging and discharging process, storage of the ammonium ions can be achieved together with C = O by introducing adjacent C = N, then stability is improved, and the service life of the electrode is prolonged. And the electrochemical activity is enhanced.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of quinone derivative electrode materials, and particularly relates to a quinone derivative electrode based on C=N bond number regulation and application thereof. BACKGROUND

[0002] As a new emerging electrochemical energy storage technology, aqueous ammonium-ion batteries (AIBs) have shown great potential in renewable energy storage in recent years due to their low cost, high safety and environmental friendliness. Compared with lithium / sodium-ion batteries, ammonium ions (NH4 + ) have the advantages of abundant resources, high ionic conductivity and environmental friendliness. In addition, the hydrated ion radius of NH4 is significantly smaller than that of hydrated lithium ions and hydrated sodium ions , which provides a theoretical basis for developing high-power-density energy storage devices. However, the development of this system is still limited by the lack of high-performance electrode materials, especially electrode materials with high specific capacity, excellent cycle stability and fast reaction kinetics.

[0003] In the field of organic electrode materials, quinone compounds have become a research hotspot due to their reversible redox characteristics. It is worth noting that quinone compounds are also considered as potential ammonium ion storage materials. Current research mainly focuses on C=O storage, and in the C=O storage structure, the introduction of C=N bonds can adjust the electronic structure, ion diffusion path and stability of the material, thereby improving the electrochemical performance.

[0004] In summary, exploring the influence of the number of C=N bonds on the storage behavior of NH4 + and developing quinone derivative electrode materials with controllable structure and excellent performance can provide assistance for further designing high-performance aqueous ammonium-ion battery electrodes. SUMMARY

[0005] The purpose of the present application is to provide a quinone derivative electrode based on C=N bond number regulation and application thereof. The quinone derivative electrode relies on the formation and rupture of hydrogen bonds between ammonium ions and C=O during charging and discharging to store energy. By introducing adjacent C=N, the storage of ammonium ions can be realized together with C=O, thereby realizing the functions of improving stability and enhancing electrochemical activity.

[0006] To achieve the above purpose, the present application provides a quinone derivative electrode based on C=N bond number regulation, and the structure of the quinone derivative electrode includes one of the following general structures:

[0007]

[0008] In general formula 1 and general formula 2, the Ar group includes aromatic hydrocarbons and heterocyclic aromatic hydrocarbons, wherein Ar1 and Ar2 groups are the same or different; the R group includes H, halogen, alkyl, haloalkyl, amino, hydroxyl, alkoxy, ester, acyl, cyano, aromatic hydrocarbons, heterocyclic aromatic hydrocarbons, wherein R l and R2 groups are the same or different.

[0009] Preferably, the aromatic hydrocarbons are monocyclic or fused ring aromatic hydrocarbons, including benzene, naphthalene, anthracene, phenanthrene, pyrene, chrysene, fluorene and their substituted derivatives.

[0010] Preferably, the heterocyclic aromatic hydrocarbons are monocyclic or fused ring aromatic hydrocarbons, including pyrrole, furan, thiophene, thiazole, diazole, triazole, pyridine, pyrimidine, pyridazine, pyrazine, quinoline, isoquinoline, quinoxaline, phthalazine, benzothiazole, benzodiazole, phenanthroline, carbazole, phosphofluorene, silafluorene, phenothiazine and their substituted derivatives; the substituents include halogen, alkyl, haloalkyl, amino, hydroxyl, alkoxy, acyl, ester, amino, carbonate, aromatic group or heterocyclic aromatic group.

[0011] The application also provides a quinone derivative electrode based on the number of C=N bonds for regulating the application of negative electrode material electrode sheet in aqueous ammonium ion battery.

[0012] Preferably, the quinone derivative has at least one C=O unit and is a fused ring structure; the ammonium ion electrolyte solution in the aqueous ammonium ion battery is prepared from one or more of ammonium acetate, ammonium sulfate, ammonium chloride, and ammonium triflate.

[0013] Preferably, the preparation of the negative electrode material electrode sheet includes the following steps:

[0014] Step S1, uniformly mix the quinone derivative, ketjen black and binder to form an electrode slurry; wherein the mass ratio of the quinone derivative, ketjen black and binder is 6:3:1;

[0015] Step S2, uniformly apply the electrode slurry on the current collector to form an electrode sheet;

[0016] Step S3, place the electrode sheet in a vacuum drying oven for drying; the drying temperature is 60-80℃, and the drying time is 8-12h to obtain the negative electrode material electrode sheet.

[0017] Preferably, the quinone derivative includes 1,4-naphthoquinone, 5,8-quinoline dione, quinoxaline-5,8-dione; the binder includes polyvinylidene fluoride binder.

[0018] Preferably, the test method of the negative electrode material electrode sheet is specifically as follows: taking the negative electrode material electrode sheet as a working electrode, a platinum sheet as a counter electrode, Ag / AgCl as a reference electrode, and NH4Ac or N2H8SO4 as an electrolyte solution to form a three-electrode system, and then performing electrochemical performance test of the negative electrode material.

[0019] Preferably, the preparation of the three-electrode system comprises the following steps:

[0020] Step S1, inserting a platinum sheet counter electrode and injecting NH4Ac or N2H8SO4 as an electrolyte;

[0021] Step S2, fixing the negative electrode material electrode sheet in the electrolyte with a platinum sheet electrode clamp;

[0022] Step S3, inserting an Ag / AgCl reference electrode;

[0023] Step S4, the three-electrode system, and then performing electrochemical test.

[0024] Preferably, the concentration of the NH4Ac solution is 1M, and the concentration of the N2H8SO4 solution is 0.5M.

[0025] The above-mentioned quinone derivative electrode based on the number of C=N bonds and the application thereof have the following beneficial effects:

[0026] (1) The quinone derivative-based aqueous ammonium ion battery electrode in the application can realize electrochemical insertion and extraction of ammonium ions in an ammonium ion aqueous electrolyte solution and an atmospheric environment through the common storage of C=N and C=O to ammonium ions.

[0027] (2) The electrode material in the application can store energy through the formation and breaking of hydrogen bonds between ammonium ions and C=O in the charging and discharging process, and can realize the storage of ammonium ions together with C=O by introducing adjacent C=N, thereby improving stability and enhancing electrochemical activity.

[0028] (3) The application respectively uses 1,4-naphthoquinone, 5,8-quinoline dione and quinoxaline-5,8-dione as active substances to prepare corresponding electrode sheets, and performs electrochemical test under 1M NH4Ac and 0.5M N2H8SO4 electrolyte, respectively. The introduction of C=N can adjust the electronic activity and exhibit the performance of storing ammonium ions together with C=O, but at the same time, the solubility in the aqueous electrolyte will be increased due to the change of the combination mode.

[0029] Among them, 5,8-quinoline dione shows better electrochemical performance than 1,4-naphthoquinone, and the discharge specific capacity is 193.4mAh g -1 at a current density of 0.1Ag -1 . -1-1 The discharge specific capacity can still reach 60.5 mAh g -1 While quinoxaline-5,8-dione has poor performance, it can be speculated that the introduction of two C=N may lead to more serious dissolution in aqueous electrolyte.

[0030] (4) The present application introduces 0, 1, and 2 C=N into 1, 4-naphthoquinone materials respectively, tests the corresponding electrochemical performance in ammonium acetate and ammonium sulfate electrolyte respectively, and explores the energy storage mechanism of aqueous ammonium ion battery.

[0031] The technical solutions of the present application will be further described in detail below by means of the accompanying drawings and examples. BRIEF DESCRIPTION OF DRAWINGS

[0032] Figure 1 The structural schematic diagram of 1, 4-naphthoquinone, 5, 8-quinoline dione, and quinoxaline-5, 8-dione in the quinone derivative electrode based on the number of C=N bonds and its application embodiment of the present application; wherein a is 1, 4-naphthoquinone, b is 5, 8-quinoline dione, and c is quinoxaline-5, 8-dione;

[0033] Figure 2 The charge-discharge curve diagram of the aqueous ammonium ion battery electrode based on 1, 4-naphthoquinone, 5, 8-quinoline dione, and quinoxaline-5, 8-dione in the quinone derivative electrode based on the number of C=N bonds and its application embodiment of the present application; wherein a is 1, 4-naphthoquinone, electrolyte 1M NH4Ac, b is 5, 8-quinoline dione, electrolyte 1M NH4Ac, c is quinoxaline-5, 8-dione, electrolyte 1M NH4Ac, d is 1, 4-naphthoquinone, electrolyte 0.5M N2H8SO, e is 5, 8-quinoline dione, electrolyte 0.5M N2H8SO, and f is quinoxaline-5, 8-dione, electrolyte 0.5M N2H8SO;

[0034] Figure 3 The charge-discharge curve diagram of the aqueous ammonium ion battery electrode based on 1, 4-naphthoquinone, 5, 8-quinoline dione, and quinoxaline-5, 8-dione in the quinone derivative electrode based on the number of C=N bonds and its application embodiment of the present application; wherein a is electrolyte 1M NH4Ac, and b is electrolyte 0.5M N2H8SO4. DETAILED DESCRIPTION

[0035] The technical solutions of the present application will be further described in detail below by means of the accompanying drawings and examples.

[0036] Unless otherwise defined, the technical terms or scientific terms used in the present application shall have the usual meanings understood by those skilled in the art to which the present application belongs.

[0037] In the present application, the quinone derivatives preferably include at least one of 1,4-naphthoquinone, 5,8-quinolinedione, quinoxaline-5,8-dione. The present application does not have special limitations on the source of 1,4-naphthoquinone, 5,8-quinolinedione, quinoxaline-5,8-dione, and conventional commercially available products in the art can be used.

[0038] A quinone derivative electrode based on the number of C=N bonds includes one of the following structural general formula:

[0039]

[0040] In formula 1 and formula 2, the Ar group includes aromatic hydrocarbons and heterocyclic aromatic hydrocarbons, wherein Ar1 and Ar2 groups are the same or different; the R group includes H, halogen, alkyl, halogenated alkyl, amino, hydroxyl, alkoxy, ester, acyl, cyano, aromatic hydrocarbon, heterocyclic aromatic hydrocarbon, wherein R l and R2 groups are the same or different.

[0041] Aromatic hydrocarbons are monocyclic or fused ring aromatic hydrocarbons, including benzene, naphthalene, anthracene, phenanthrene, pyrene, azulene, fluorene and their derivatives containing substituents.

[0042] Heterocyclic aromatic hydrocarbons are monocyclic or fused ring aromatic hydrocarbons, including pyrrole, furan, thiophene, thiazole, diazole, triazole, pyridine, pyrimidine, pyridazine, pyrazine, quinoline, isoquinoline, quinoxaline, phthalazine, benzothiazole, benzodiazole, phenanthroline, carbazole, phosphole, silafluorene, phenothiazine and their derivatives containing substituents; the substituents include halogen, alkyl, halogenated alkyl, amino, light base, alkoxy, alkoxy, acyl, acyl, amino, carbonic acid, aromatic group or heterocyclic aromatic group.

[0043] Application of quinone derivative electrode based on the number of C=N bonds as negative material electrode sheet in aqueous ammonium ion battery.

[0044] Examples

[0045] As Figure 1 shown, a negative material electrode sheet of an aqueous ammonium ion battery based on 1,4-naphthoquinone, 5,8-quinolinedione, quinoxaline-5,8-dione, the specific preparation includes the following steps:

[0046] Step S1, respectively, 60 mg of 1,4-naphthoquinone, 5,8-quinolinedione, quinoxaline-5,8-dione, 30 mg of Ketjen black, 10 mg of polyvinylidene fluoride binder are ground and mixed uniformly, 0.5 g of N-methyl pyrrolidone is added and stirred uniformly to form an electrode slurry;

[0047] Step S2, the electrode slurry is evenly applied on a clean stainless steel mesh to form an electrode sheet;

[0048] Step S3: Place the electrode sheet in a vacuum drying oven for drying; the drying temperature is 80° C. and the drying time is 12 hours to obtain an electrode sheet of negative electrode material for an aqueous ammonium ion battery.

[0049] The battery performance tests of aqueous ammonium ion battery electrodes based on quinone derivatives, such as charge and discharge specific capacity, coulombic efficiency, and rate performance test, are carried out in a three-electrode system.

[0050] The preparation of the three-electrode system of the negative electrode material electrode sheet of the aqueous ammonium ion battery prepared in this embodiment includes the following steps:

[0051] Step S1, inserting a platinum counter electrode, and injecting a 1M NH4Ac aqueous solution or a 0.5M N2H8SO4 aqueous solution as an electrolyte;

[0052] Step S2, fixing the negative electrode material electrode sheet of the aqueous ammonium ion battery prepared in this embodiment in the electrolyte using a platinum electrode clamp;

[0053] Step S3, inserting an Ag / AgCl reference electrode;

[0054] Step S4: obtain a three-electrode system and perform electrochemical testing.

[0055] The preparation process of the above three-electrode system is completed at room temperature in an atmospheric atmosphere without the need for an additional anhydrous and oxygen-free environment.

[0056] The electrochemical test results are as follows Figures 2-3 As shown in the figure, under the conditions of 1M NH4Ac / 0.5M N2H8SO4 as electrolyte, charge and discharge tests and rate tests were carried out at different current densities in the working range of -0.6-0.1V (vs.Ag / AgCl) / -0.5-0.3V (vs.Ag / AgCl). Among them, 5,8-quinolinedione achieved the best electrochemical performance. In 1M NH4Ac electrolyte, the charge and discharge performance was the best at 0.1, 0.2, 0.5, 1, 2, 5, and 10Ag -1 The discharge capacity at current density of 150, 120, 100, 90, 80, 70, and 60 mAh g -1 In 0.5M N2H8SO4 electrolyte, at 0.1, 0.2, 0.5, 1, 2, 5, 10Ag -1 The discharge capacity at current density of 100, 80, 60, 50, 30, and 20 mAh g -1 .

[0057] Therefore, the application adopts the above-mentioned quinone derivative electrode based on the number of C=N bonds and application thereof. The quinone derivative electrode relies on the formation and rupture of hydrogen bonds between ammonium ions and C=O in the charging and discharging process to store energy. By introducing adjacent C=N, the storage of ammonium ions can be realized together with C=O, thereby realizing the functions of improving stability and enhancing electrochemical activity.

[0058] Finally, it should be noted that the above examples are only used to illustrate the technical solutions of the present application and not to limit them. Although the present application 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 application can still be modified or replaced by equivalents, and these modifications or equivalent replacements should not make the modified technical solutions deviate from the spirit and scope of the technical solutions of the present application.

Claims

1. A quinone derivative electrode based on the regulation of the number of C=N bonds, characterized in that: The structure of the quinone derivative electrode includes one of the following general structural formulas: In general formula 1 and general formula 2, the Ar group includes aromatic hydrocarbons and heterocyclic aromatic hydrocarbons, wherein the Ar1 and Ar2 groups are the same or different; the R group includes H, halogen, alkyl, haloalkyl, amino, hydroxyl, alkoxy, ester, acyl, cyano, aromatic hydrocarbon, heterocyclic aromatic hydrocarbon, wherein R l and R2 groups are the same or different.

2. The quinone derivative electrode based on C=N bond number regulation according to claim 1, characterized in that: Aromatic hydrocarbons are monocyclic or condensed-ring aromatic hydrocarbons, including benzene, naphthalene, anthracene, phenanthrene, pyrene, perylene, fluorene, and their substituted derivatives.

3. The quinone derivative electrode based on C=N bond number regulation according to claim 1, characterized in that: Heterocyclic aromatic hydrocarbons are monocyclic or condensed-ring aromatic hydrocarbons, including pyrrole, furan, thiophene, thiazole, diazole, triazole, pyridine, pyrimidine, pyridazine, pyrazine, quinoline, isoquinoline, quinoxaline, phthalazine, benzothiazole, benzodiazole, phenanthroline, carbazole, phosphorene, silylfluorene, phenothiazine, and derivatives thereof containing substituents; the substituents include halogen, alkyl, haloalkyl, amino, hydroxy, alkoxy, mercapto, ester, acyl, amino, carbonate, aromatic, or heterocyclic aromatic groups.

4. Use of the quinone derivative electrode based on the regulation of the number of C=N bonds according to any one of claims 1 to 3 as a negative electrode material electrode sheet in an aqueous ammonium ion battery.

5. The use according to claim 4, characterized in that: The quinone derivative has at least one C=O unit and is a fused ring structure; the ammonium ion electrolyte solution in the aqueous ammonium ion battery is an aqueous solution prepared with one or more of ammonium acetate, ammonium sulfate, ammonium chloride, and ammonium trifluoromethanesulfonate, wherein the concentration of the ammonium salt is 0.5M-2M.

6. The use according to claim 4, characterized in that The preparation of the negative electrode material electrode sheet includes the following steps: Step S1, uniformly mixing a quinone derivative, Ketjen black, and a binder to form an electrode slurry; wherein the mass ratio of the quinone derivative, Ketjen black, and the binder is 6:3:1; Step S2: evenly apply the electrode slurry on the current collector to form an electrode sheet; Step S3: Place the electrode sheet in a vacuum drying oven for drying; the drying temperature is 60-80° C., and the drying time is 8-12 hours to obtain a negative electrode material electrode sheet.

7. The use according to claim 6, characterized in that: The quinone derivatives include 1,4-naphthoquinone, 5,8-quinolinedione, and quinoxaline-5,8-dione; and the binder includes polyvinylidene fluoride binder.

8. The use according to claim 4, characterized in that The specific testing method for the negative electrode material electrode sheet is as follows: the negative electrode material electrode sheet is used as the working electrode, the platinum sheet is used as the counter electrode, Ag / AgCl is used as the reference electrode, and NH4Ac or N2H8SO4 is used as the electrolyte solution to form a three-electrode system to test the electrochemical performance of the negative electrode material.

9. The use according to claim 8, characterized in that: The preparation of the three-electrode system includes the following steps: Step S1, inserting a platinum counter electrode and injecting NH4Ac or N2H8SO4 as the electrolyte; Step S2, fixing the negative electrode material electrode sheet in the electrolyte with a platinum electrode clamp; Step S3, inserting an Ag / AgCl reference electrode; Step S4: three-electrode system for electrochemical testing.

10. The use according to claim 9, characterized in that: The concentration of NH4Ac solution is 1M, and the concentration of N2H8SO4 solution is 0.5M.

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