Naphthalimide-containing polycarbonyl organic electrode materials and their applications in metal ion batteries

Abstract

The present invention belongs to the field of metal ion battery electrode materials, and specifically discloses a polycarbonyl organic electrode material containing naphthalene imide and its application in metal ion batteries. The polycarbonyl organic electrode material is obtained by reacting 1,4,5,8-naphthalenetetracarboxylic anhydride with 2,5-dimethoxyaniline and then oxidizing it. Using the polycarbonyl organic compound as a zinc ion battery electrode material, a specific capacity of up to 1100mAh / g can be achieved, and at a high voltage of 2.0V and a current density of 1A / g, a specific capacity of up to 250mAh / g can be achieved, and the total number of stable cycles exceeds 4000. In addition, using the polycarbonyl compound as a lithium ion battery electrode material, a specific capacity of up to 651mAh / g and excellent stability can be achieved. The polycarbonyl organic electrode material containing naphthalene imide provided by the present invention has good application prospects in metal ion battery systems.

Description

Technical Field

[0001] The present invention relates to the field of metal ion battery electrode materials, in particular to a naphthaleneimide-containing polycarbonyl organic electrode material and application thereof in metal ion batteries. Background Art

[0002] The development of high-performance, long-life, and low-cost secondary batteries plays a vital role in addressing the global energy crisis and environmental pollution, and is a key research direction in the current new energy field. Within the field of secondary battery research, lithium-ion batteries have been extensively studied due to their high energy density, long cycle life, and lack of memory effect, and are widely used in fields such as electric vehicles and smartphones. However, the specific capacity of lithium batteries currently available on the market is approximately 100-300 mAh / g. With the rapid development of the market, this has become difficult to meet the demand for higher capacity, and further development of high-capacity, long-life, low-cost, and highly safe lithium-ion batteries is urgently needed.

[0003] In addition, zinc-ion batteries, as a new type of secondary battery, have also attracted extensive attention and research due to their advantages such as low cost, high safety and good environmental protection. At present, the performance of zinc-ion batteries has made certain progress, but there is still a certain gap compared with lithium-ion batteries, mainly manifested in low specific capacity, usually between 50-150mAh / g. For example, zinc-manganese batteries: the specific capacity is about 50-80mAh / g, and the cycle life is short. Moreover, for aqueous zinc-ion batteries, due to the decomposition of water, it is difficult to develop high-voltage aqueous zinc batteries. In short, the development of aqueous zinc batteries with high voltage, high capacity and excellent cycle stability still faces great challenges.

[0004] In particular, organic materials with excellent redox activity are easy to obtain and cheap, and their structures are rich and adjustable. As electrode active materials, they can also present high specific capacity. In view of this, it is of great significance to develop cheap and high-performance organic electrode materials for application in metal ion batteries. At present, some excellent performance zinc ion organic electrode materials (Angewandte Chemie, 2022, 134 (51): e202214244; Science advances, 2018, 4 (3): eaao1761.) and lithium ion organic electrode materials (CN 110429279A, Materials Today 50 (2021): 170-198, ACS Applied Polymer Materials 5.11 (2023): 9128-9137.) have been developed, but the specific capacity, long cycle performance and rate performance of related organic electrode materials still need to be further improved. Moreover, few high-performance organic electrode materials that can be applied to both zinc ion batteries and lithium ion batteries have been developed. Summary of the Invention

[0005] To address the above problems, the present invention has developed an organic electrode material with multiple active sites, which has a low solubility in both organic solvents and water. It is then applied to zinc-ion batteries and lithium-ion batteries, achieving high specific capacity, long cycle life, and high rate performance.

[0006] The present invention provides a polycarbonyl organic electrode material containing naphthaleneimide, applicable to metal zinc-ion batteries and lithium-ion batteries. The material incorporates redox-active naphthaleneimide and benzoquinone units, utilizing multiple active sites within the structure to achieve a high specific capacity. Furthermore, the material forms a large planar structure, which reduces its solubility in water or organic solvents, facilitating stable cycling performance and excellent rate capability. This simple organic electrode material, with readily available raw materials, is simple to synthesize, and has a high yield. Furthermore, the material can achieve high energy density, good cycling stability, and excellent overall electrochemical performance in zinc-ion and lithium-ion battery systems, demonstrating promising application prospects.

[0007] The polycarbonyl organic electrode material containing naphthalene imide provided by the present invention has a structural formula as shown in Formula D1:

[0008]

[0009] The present invention also provides a method for preparing the above-mentioned polycarbonyl organic electrode material containing naphthalene imide: 1,4,5,8-naphthalenetetracarboxylic anhydride and 2,5-dimethoxyaniline are dissolved in DMF (N,N-dimethylformamide), heated to 100-150°C, stirred and refluxed for reaction for 10 hours, after the reaction is completed, washed with DMF and ethanol multiple times, and dried to obtain a product precursor, the precursor and ammonium cerium nitrate are dissolved in a mixed solution of deionized water and acetonitrile (volume ratio of 2:8), stirred and reacted at room temperature for 2 hours, after the reaction is completed, washed with ethanol and deionized water multiple times, and dried to obtain the target product D1.

[0010] The reaction formula for preparing polycarbonyl organic electrode materials is as follows:

[0011]

[0012] The molar ratio of 1,4,5,8-naphthalenetetracarboxylic anhydride to 2,5-dimethoxyaniline is 1:2 to 2.5.

[0013] The molar ratio of the precursor to the ammonium cerium nitrate is 1:4-5.

[0014] The polycarbonyl organic electrode material of the present invention is used to prepare the positive electrode of a zinc ion battery. When used in the positive electrode of a zinc ion battery, the current collector can be graphite paper, and the electrolyte can be sulfuric acid, zinc sulfate, or zinc sulfonate.

[0015] The method for preparing the battery electrode material used in zinc ion batteries is as follows:

[0016] D1 material, PVDF, acetylene black and / or carbon nanotubes are mixed together in a certain mass ratio and ground together. After the mixture is evenly mixed, an appropriate amount of N-methyl-2-pyrrolidone (NMP) is added and ground into a paste slurry, which is then coated on graphite paper and vacuum-dried at 80°C for 12 hours to prepare a battery electrode sheet (D1 composite material). The composite material is used as the positive electrode, Whatman glass fiber separator GF / D is used as the battery separator, sulfuric acid, zinc sulfate and zinc sulfonate are used as the electrolyte, respectively, and a zinc sheet is used as the negative electrode. A button battery is assembled using conventional technology.

[0017] The polycarbonyl organic electrode material of the present invention can also be used to prepare a positive electrode for a lithium-ion battery. The current collector used to prepare the positive electrode for the lithium-ion battery is aluminum foil, and the electrolyte is 1 mol / L lithium bis(trifluoromethylsulfonyl)imide.

[0018] The method for preparing the battery electrode material used in the preparation of lithium-ion batteries is as follows:

[0019] The product D1, acetylene black and binder polyvinylidene fluoride (PVDF) were mixed in a certain mass ratio, ground and mixed into a slurry with N-methylpyrrolidone (NMP) as a solvent, and then evenly coated on the current collector aluminum foil. Then, it was dried in a vacuum drying oven at 80°C to obtain a battery electrode (D1 composite material). The dried electrode was cut into a round piece with a diameter of 12 mm; a metal lithium sheet was used as the negative electrode, the D1 composite material was used as the positive electrode, the separator was Ce1grad 2550, and the electrolyte used was 1 mol / L lithium bistrifluoromethanesulfonyl imide (LiTFSI). The electrolyte in the electrolyte was lithium bistrifluoromethanesulfonyl imide; the electrolyte solvent was a mixed solvent of 1,3-dioxolane (DOL) and ethylene glycol dimethyl ether (DME). The battery was assembled in a glove box filled with argon protection.

[0020] The advantages of the present invention are that the polycarbonyl organic electrode material can be used as a multifunctional electrode material to construct zinc-ion batteries with a specific capacity of up to 1100 mAh / g and lithium-ion batteries with a specific capacity of up to 651 mAh / g. In particular, the zinc-ion batteries can achieve long-life cycles at a high voltage of 2.0 V. The polycarbonyl organic electrode material has low solubility in water and organic solvents, exhibits good structural stability during charge and discharge, and exhibits excellent rate performance. The polycarbonyl organic electrode material is readily available, easy to synthesize, has high yield, and is environmentally friendly. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 Multiple constant current charge-discharge curves of a zinc ion battery using Example D1 as the electrode active material at 50 mA / g, where the values ​​1, 3, 30, and 100 correspond to different cycle numbers, respectively.

[0022] Figure 2 This is the long cycle specific capacity of a zinc ion battery using Example D1 as the electrode active material at 50 mA / g.

[0023] Figure 3 The constant current charge and discharge capacity of the zinc ion battery using Example D1 as the electrode active material at different current densities.

[0024] Figure 4 The long cycle of the zinc ion battery using Example D1 as the electrode active material at a current density of 1000 mA / g and different cut-off voltages.

[0025] Figure 5 The cycle specific capacity of the zinc ion battery using Example D1 as the electrode active material at a current density of 1 A / g with cut-off voltages of 0.2-1.6 V, 0.15-1.8 V, 0.15-1.9 V, and 0.1-2.0 V.

[0026] Figure 6 This is the cycling curve of a zinc ion battery using Example D1 as the electrode active material at a high cut-off voltage of 2V.

[0027] Figure 7 This is the long cycle specific capacity of a lithium ion battery using Example D1 as the electrode active material at 50 mA / g. DETAILED DESCRIPTION

[0028] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention will be further described in detail below in conjunction with the embodiments. It should be noted that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0029] Example 1

[0030] A method for preparing a zinc ion battery electrode material comprises the following steps:

[0031] Take (1g) 3.73mmol of 4,5,8-naphthalenetetracarboxylic anhydride and (1.2g) 7.84mmol of 2,5-dimethoxyaniline and dissolve them in DMF (N,N-dimethylformamide), reflux at 140°C for 10h, wash with DMF and then with ethanol three times after the reaction, and dry to obtain 1.55g of the product precursor. Take 1g (1.857mmol) of the precursor and dissolve it in 15mL of a mixed solvent of deionized water and acetonitrile, add 5.09g (9.285mmol) of ammonium cerium nitrate and mix (wherein, the mass ratio of the precursor to ammonium cerium nitrate is 1:5, and the volume ratio of water to acetonitrile is 2:8), stir at room temperature for 2h, after which the reaction is completed, wash with deionized water and then with ethanol until the washing liquid is colorless, and dry to obtain the target product D1 with a yield of 91%.

[0032] Take 50 mg of product D1, 40 mg of acetylene black and 10 mg of PVDF (a total of 100 mg) (mass ratio of 5:4:1) and grind them together. After mixing evenly, add 1 ml of NMP and grind them into a paste. The paste is evenly coated on graphite paper at a density of 1 mg / cm 2 The battery was then dried in an 80°C oven for 12 hours. The dried electrode was then cut into 12mm diameter discs. This electrode served as the positive electrode, a Whatman glass fiber separator GF / D was used as the separator, 0.5M H2SO4 was used as the electrolyte, and a zinc sheet was used as the negative electrode. The battery was assembled using conventional techniques.

[0033] The button cell assembled according to this method was subjected to charge and discharge cycle tests in the voltage range of 0.1-1.6V. The curve (eg Figure 1 , Figure 2 ), the test results show that the electrode material can achieve a specific capacity of up to 1100mAh / g (such as Figure 1 , Figure 2 ).

[0034] Example 2

[0035] The zinc ion battery electrode material D1 was prepared according to the steps of Example 1.

[0036] Preparation of zinc ion battery electrode materials and testing of their electrochemical performance;

[0037] Take 50 mg of D1, 30 mg of acetylene black, 10 mg of PVDF and 10 mg of carbon nanotubes (a total of 100 mg) (mass ratio of 5:3:1:1) and grind them together. After mixing evenly, add 1 ml of NMP and grind into a uniform slurry. Apply it on graphite paper at a density of 1 mg / cm 2 The battery was then dried in an 80°C oven for 12 hours. The dried electrode was then cut into 12mm diameter discs. This electrode was used as the positive electrode, Whatman GF / D fiberglass separator as the separator, 0.3M zinc sulfonate as the electrolyte, and a zinc sheet as the negative electrode. The battery was assembled using conventional techniques.

[0038] When the battery voltage was tested at a rate within the range of 0.2-1.6V, it was found that the battery's reversible discharge capacity was 210mAh / g at a current density of 50mA / g. As the battery operating current reached 100mA / g, the battery's reversible discharge capacity reached 190mAh / g. When the current density reached 200mA / g, the battery's reversible discharge capacity was 180mAh / g. When the battery operating current reached 300mA / g, the battery's reversible discharge capacity could still reach 170mAh / g. When the current density reached 400mA / g, the battery's reversible discharge capacity was 160mAh / g. When the battery operating current reached 500mA / g, the battery's reversible discharge capacity could still reach 150mAh / g. When the current density reached 1000mA / g, the battery's reversible discharge capacity was 125mAh / g. When the current density reached 2000mA / g, the battery's reversible discharge capacity was 80mAh / g. Finally, when the current density was adjusted back to 50 mA / g, the capacity returned to 215 mAh / g, indicating that the electrode material has good rate performance (such as Figure 3 ).

[0039] The battery was charged and discharged with a high current, the current density was set to 1A / g, the cut-off voltage was set to 1.6V, 1.8V, 1.9V, 2.0V and the long cycle was more than 4000 cycles (such as Figure 4 ).

[0040] At different cut-off voltages of 1.6V, 1.8V, 1.9V, and 2.0V, and a current density of 1A / g, the charge and discharge curves show that the greater the cut-off voltage, the greater the battery specific capacity (e.g. Figure 5 ). At a cut-off voltage of 2V, a current density of 1A / g was achieved to achieve a specific capacity of 250mAh / g (such as Figure 6 ).

[0041] Example 3

[0042] The zinc ion battery electrode material D1 was prepared according to the steps of Example 1;

[0043] A zinc ion battery, made of the zinc ion electrode material, and its electrochemical performance test;

[0044] The assembly method and active material ratio are the same as those in Example 2, and 0.5M H2SO4 is used as the electrolyte.

[0045] The battery made in this example was tested for its charge-discharge capacity and cycling characteristics. After 100 cycles, the specific capacity remained around 190 mAh / g, and the coulombic efficiency remained above 90%.

[0046] Example 4

[0047] The zinc ion battery electrode material D1 was prepared according to the steps of Example 1;

[0048] A zinc ion battery, made of the zinc ion electrode material, and its electrochemical performance test;

[0049] The assembly method and active material ratio are the same as those in Example 2, and 1.5M H2SO4 is used as the electrolyte.

[0050] The battery made in this example was tested for its charge-discharge capacity and cycle characteristics. After 100 cycles, the specific capacity remained around 180 mAh / g, and the coulombic efficiency remained above 90%.

[0051] Example 5

[0052] The zinc ion battery electrode material D1 was prepared according to the steps of Example 1;

[0053] A zinc ion battery, made of the zinc ion electrode material, and its electrochemical performance test;

[0054] The assembly method and active ingredient ratio were similar to those in Example 2, and 2M zinc sulfonate was used as the electrolyte.

[0055] The battery made in this example was tested for its charge-discharge capacity and cycling characteristics. After 100 cycles, the specific capacity remained around 110 mAh / g, and the coulombic efficiency remained above 85%.

[0056] Example 6

[0057] The zinc ion battery electrode material D1 was prepared according to the steps of Example 1;

[0058] A zinc ion battery, made of the zinc ion electrode material, and its electrochemical performance test;

[0059] The assembly method and active ingredient ratio were similar to those in Example 2, and 3M zinc sulfate was used as the electrolyte.

[0060] The battery made in this example was tested for its charge-discharge capacity and cycling characteristics. After 100 cycles, the specific capacity remained around 180 mAh / g, and the coulombic efficiency remained above 80%.

[0061] Example 7

[0062] The lithium-ion battery electrode material D1 was prepared according to the steps of Example 1.

[0063] Lithium-ion batteries, made of the lithium-ion electrode materials, and their electrochemical performance tests;

[0064] Take 50 mg of product D1, 40 mg of acetylene black and 10 mg of binder polyvinylidene fluoride (PVDF) to mix, totaling 100 mg (mass ratio of 5:4:1), use 0.5 ml of N-methylpyrrolidone (NMP) as solvent, grind and mix into slurry, and evenly coat it on the current collector aluminum foil at a thickness of 1 mg / cm 2 Then, the electrodes were dried in a vacuum drying oven at 80°C for 12 hours, and the dried electrodes were cut into discs with a diameter of 12 mm. The metal lithium sheet was used as the negative electrode, the D1 composite material was used as the positive electrode, and the Ce1grad2550 provided by Cluder was used as the separator. The electrolyte used was 1 mol / L lithium bis(trifluoromethylsulfonyl)imide (LiTFSI). The electrolyte in the electrolyte was lithium bis(trifluoromethylsulfonyl)imide. The electrolyte solvent was a mixed solvent of 1,3-dioxolane (DOL) and ethylene glycol dimethyl ether (DME) with a volume ratio of 1:1. The battery was assembled into a battery using a conventional battery assembly process in a glove box filled with argon protection.

[0065] The battery made in this example was tested for its charge and discharge capacity and cycle characteristics. After 275 cycles, the specific capacity gradually increased from the original 120mAh / g. At 384 cycles, the capacity reached 651mAh / g, and the coulombic efficiency was always above 80%. Figure 7 ).

Claims

1. A polycarbonyl organic electrode material containing naphthalene imide, characterized in that: The structural formula of the electrode material is shown in Formula D1:

2. The polycarbonyl organic electrode material containing naphthalene imide according to claim 1, wherein: The preparation method of the electrode material comprises the following steps: dissolving 1,4,5,8-naphthalenetetracarboxylic anhydride and 2,5-dimethoxyaniline in N,N-dimethylformamide, heating and refluxing the mixture, washing the mixture with N,N-dimethylformamide and ethanol, and drying the mixture to obtain a precursor; then mixing the precursor with a cerium ammonium nitrate solution dissolved in a mixed solvent of deionized water and acetonitrile, stirring the mixture at room temperature for 2 hours, and washing the mixture with ethanol and deionized water, and drying the mixture to obtain the target product D1.

3. The polycarbonyl organic electrode material containing naphthalene imide according to claim 2, wherein: The molar ratio of 1,4,5,8-naphthalenetetracarboxylic anhydride to 2,5-dimethoxyaniline is 1:2-2.5, and the molar ratio of the precursor to ceric ammonium nitrate is 1:4-5.

4. The polycarbonyl organic electrode material containing naphthalene imide according to claim 2, wherein: The heating reflux reaction is carried out by stirring at 100-150° C. for 10 hours.

5. A use of the polycarbonyl organic electrode material containing naphthalene imide according to claim 1, characterized in that: The electrode material is used for preparing the positive electrode of a metal ion battery.

6. The use of the polycarbonyl organic electrode material containing naphthalene imide according to claim 5, characterized in that: The metal ion battery positive electrode is: a zinc ion battery positive electrode or a lithium ion battery positive electrode.

7. The use of the polycarbonyl organic electrode material containing naphthalene imide according to claim 6, characterized in that: Used to prepare the positive electrode of zinc ion battery, the current collector is graphite paper, and the electrolyte is 0.5-1.5M sulfuric acid, 3M zinc sulfate, and 0.3-2M zinc sulfonate.

8. The use of the polycarbonyl organic electrode material containing naphthalene imide according to claim 6, characterized in that: Used to prepare the positive electrode of lithium-ion batteries, the current collector is aluminum foil and the electrolyte is 1 mol / L lithium bis(trifluoromethylsulfonyl)imide.

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