1,4,5,8-phenanthrene diquinone active material, organic cathode material and aqueous zinc battery

Abstract

The present invention discloses a 1,4,5,8-phenanthrene diquinone active substance, an organic positive electrode material and an aqueous zinc battery. The organic positive electrode material containing the 1,4,5,8-phenanthrene diquinone active substance designed in the present application has a π conjugated structure, and utilizes carbonyl and Zn 2+ The reversible redox reaction between the two materials realizes the rapid storage of electrical energy, making it have excellent conductivity and structural stability, significantly improving the specific capacity, energy density and cycle stability of organic positive electrode materials. Specifically, the aqueous zinc battery electrode based on 1,4,5,8-phenanthrene diquinone active material is 0.64A g ‑1 The maximum specific capacity at the current density is 412.28 mAh g ‑1 When the current increases 100 times, the specific capacity is still 138.95 mAh g ‑1 At the same time, the aqueous zinc battery is at 5.13A g ‑1 After 1000 cycles at a current density of 222.11 mAh g ‑1 The specific capacity of the battery is as high as 71.62%, and the coulombic efficiency is still 100% after 1000 cycles, showing excellent electrochemical performance.

Description

Technical Field

[0001] The present invention belongs to the technical field of electrochemical power sources, and in particular relates to a 1,4,5,8-phenanthrene diquinone active substance, an organic positive electrode material and an aqueous zinc battery. Background Art

[0002] With the increasing global demand for energy and the increasingly serious environmental pollution problem, the development of new and efficient energy storage systems has become particularly urgent. Among the many energy storage technologies, aqueous zinc batteries have attracted widespread attention due to their low cost, high safety and environmental friendliness. Aqueous zinc batteries use metallic zinc as the negative electrode and aqueous solution as the electrolyte, and have a high theoretical specific capacity (820mAh g -1 ) and a moderate redox potential (-0.76 V versus standard hydrogen electrode), which makes aqueous zinc batteries an ideal candidate for large-scale energy storage applications.

[0003] Despite the aforementioned advantages, aqueous zinc batteries still face several challenges in their commercialization, particularly the performance limitations of cathode materials. Existing inorganic cathode materials, such as manganese-based oxides, vanadium-based compounds, and Prussian blue analogs, often suffer from low energy density, poor cycling stability, or high production costs. Furthermore, these materials often undergo irreversible structural changes during charge and discharge, leading to rapid capacity degradation.

[0004] In recent years, organic electrode materials have been favored by researchers due to their structural diversity, sustainability, and relatively high theoretical specific capacity. Their functional groups can undergo reversible redox reactions with zinc ions to achieve the storage and output of electrical energy. Organic materials can be divided into p-type, n-type, and bipolar types according to the charge properties of the functional groups. P-type organic materials have a high platform discharge voltage (>1.0Vvs.Zn / Zn 2+ ), but its low active site density and single-electron reactive groups lead to limited capacity output (<150 mAh g -1 Bipolar organic materials combine the advantages of high voltage and capacity of p-type and n-type organic materials, but are still in the primary research stage, and their low active site density and single-electron reactive groups lead to insufficient capacity (<200mAh g -1 ) and low energy density (<150Wh kg -1 ), a tetranitroporphyrin reported so far has an energy density of up to 365Wh kg -1 ;N-type organic materials usually include quinone compounds, nitroaromatics, azo compounds and imine compounds. Quinone compounds are widely found in nature and are considered to be a potential green electrode material. Quinone compounds usually have excellent specific capacity (120-336mAh g -1), but its platform discharge voltage is low (<0.8Vvs.Zn / Zn 2+ ) resulting in insufficient energy density (mostly between 200-260Wh kg -1 ), very few quinone compounds can provide high discharge voltage (1.1V), but their insufficient capacity still leads to low energy density and other problems. The main reason is that the inherent energy level of their lowest unoccupied molecular orbital and the low utilization rate of carbonyl active units are low. For example, 9,10-phenanthrenequinone and 9,10-anthraquinone have a platform discharge voltage of only 0.57V and 0.51V due to their inherent energy level of the lowest unoccupied molecular orbital, and their theoretical specific capacity is 258mAh g -1 Due to the low utilization of carbonyl active units (43% for 9,10-phenanthrenequinone and 75% for 9,10-anthraquinone), its actual capacity is only 110 mAh g -1 and 193mAh g -1 Therefore, in order to solve these problems, the key to improving the performance of zinc batteries and promoting their commercial application is to select quinone compounds with large theoretical capacity, multiple electrons and high active unit utilization through molecular design and structural optimization. Summary of the Invention

[0005] The present invention aims to at least partially address one of the technical problems in the related art. To this end, the present invention primarily provides a 1,4,5,8-phenanthrene diquinone active material, an organic cathode material, and an aqueous zinc battery. The organic cathode material prepared using the 1,4,5,8-phenanthrene diquinone active material exhibits high redox activity and stability. The resulting aqueous zinc battery exhibits high specific capacity, good cycle stability, and excellent rate capability, significantly improving the overall performance of the aqueous zinc battery.

[0006] The purpose of the present invention is achieved through the following technical solutions:

[0007] A 1,4,5,8-phenanthrene diquinone active substance, wherein the chemical structural formula of the 1,4,5,8-phenanthrene diquinone active substance is:

[0008]

[0009] In certain specific embodiments, the 1,4,5,8-phenanthrene diquinone active substance is obtained by the following preparation method, which specifically comprises the following steps:

[0010] A1: Dissolve 5,8-dimethoxy-1,4-phenanthranaquinone in acetonitrile to obtain a mixed solution, and heat and stir;

[0011] A2: Use an oxidant dissolved in water to form an oxidant solution;

[0012] A3: Rapidly adding the oxidant solution to the mixed solution to react and obtain a reaction solution;

[0013] A4: Add distilled water to the reaction solution and perform extraction using an extractant;

[0014] A5: Wash the organic phase after extraction with water, salt and dry it;

[0015] A6: The solvent is removed by distillation under reduced pressure, followed by drying to obtain the active substance 1,4,5,8-phenanthrene diquinone.

[0016] In certain specific embodiments, the mass ratio of the 5,8-dimethoxy-1,4-phenanthranaquinone, acetonitrile, and oxidant is 1:(70-80):(1-4); the oxidant is cerium ammonium nitrate; and the extractant is dichloromethane.

[0017] In certain embodiments, the heating condition in step A1 is 20-50°C;

[0018] The reaction parameters in step A3 are a reaction temperature of 20-50° C., stirring and maintaining for 0.25-1.5 h;

[0019] In step A5, the water washing is performed with distilled water, the salt washing is performed with a saturated sodium chloride solution, and the drying is performed with anhydrous sodium sulfate;

[0020] The temperature of the reduced pressure distillation in step A6 is 30-60° C., and the drying condition is vacuum drying at 40-80° C. for 12-36 hours.

[0021] An organic cathode material comprises the aforementioned 1,4,5,8-phenanthrene diquinone active substance.

[0022] In certain specific embodiments, the organic cathode material is prepared by the following preparation method, specifically comprising the following steps: B1: mixing the 1,4,5,8-phenanthrene diquinone active material and graphite, grinding them uniformly, and then adding a polytetrafluoroethylene solution to obtain a fluid paste slurry;

[0023] B2: The slurry is evenly coated on a current collector, and dried to obtain the organic positive electrode material.

[0024] In certain specific embodiments, the mass ratio of the 1,4,5,8-phenanthrene diquinone active material, graphite, and polytetrafluoroethylene in step B1 is: (4-8): (5-3): 1;

[0025] In certain specific embodiments, the current collector includes but is not limited to titanium foil, nickel mesh, titanium mesh, stainless steel mesh and carbon cloth.

[0026] In certain specific embodiments, the drying condition in step B2 is drying in a vacuum drying oven at 60° C. for 24 hours.

[0027] An aqueous zinc battery is assembled using the aforementioned organic positive electrode material.

[0028] In certain specific embodiments, the aqueous zinc battery is obtained by the following assembly method, which specifically comprises the following steps:

[0029] C1: the organic cathode material is used as the positive electrode, and metallic zinc is used as the negative electrode;

[0030] C2: Arrange the positive electrode and the negative electrode and place them in an electrolytic cell to assemble a battery.

[0031] In certain specific embodiments, the purity of the metallic zinc is ≥99.99%; the diaphragm material includes but is not limited to filter paper and glass fiber; the electrolyte includes but is not limited to ZnCl2, ZnSO4 or Zn(CF3SO3)2 aqueous solution, and the electrolyte concentration is 1-10M.

[0032] Compared with the prior art, the present invention has at least the following advantages:

[0033] 1) The organic cathode material containing 1,4,5,8-phenanthrene diquinone active substance designed by the present invention has a π conjugated structure and utilizes carbonyl and Zn 2+ Coordination is a 4-electron transfer reaction with an active site utilization rate of up to 92%. 2+ The reversible redox reaction occurring between them realizes the rapid storage of electrical energy, giving it excellent conductivity and structural stability, and significantly improving the specific capacity, energy density and cycle stability of organic positive electrode materials.

[0034] 2) The present invention prepared for the first time the -1 The maximum specific capacity at the current density is 412.28 mAh g -1 The aqueous zinc battery electrode based on 1,4,5,8-phenanthrene diquinone active material has a discharge platform potential of 0.88V and an energy density of up to 363Whkg -1 When the current increases 100 times, the specific capacity of the electrode is still 138.95 mAh g -1 At the same time, at 5.13A g -1 After 1000 cycles at a current density of 222.11 mAh g -1 The specific capacity of the battery is as high as 71.62%, and the coulombic efficiency is still 100% after 1000 cycles, showing excellent electrochemical performance.

[0035] 3) The main raw materials used in the present invention are widely available, low-cost and environmentally friendly. Electrode preparation, electrolyte preparation and battery assembly are all carried out at room temperature and pressure, which is safe and pollution-free, and can further reduce preparation costs. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] In order to more clearly illustrate the specific embodiments of the present invention, the following briefly introduces the drawings required for the specific embodiments or the description of the prior art.

[0037] Figure 1 This is an infrared spectrum of the 1,4,5,8-phenanthrene diquinone active substance prepared in Example 1 of the present invention;

[0038] Figure 2 The 1,4,5,8-phenanthrene diquinone active substance prepared in Example 1 of the present invention is 1 HNMR spectrum;

[0039] Figure 3 The 1,4,5,8-phenanthrene diquinone active substance prepared in Example 1 of the present invention is 13 CNMR spectrum;

[0040] Figure 4 This is a constant current charge and discharge curve diagram of the aqueous zinc battery electrode based on 1,4,5,8-phenanthrene diquinone of the present invention;

[0041] Figure 5 This is a cycle life diagram of the aqueous zinc battery electrode based on 1,4,5,8-phenanthrene diquinone of the present invention. DETAILED DESCRIPTION

[0042] The present invention will be further described in detail below with reference to the accompanying drawings and examples. The following examples are merely illustrative and non-restrictive, and should not be used to limit the scope of protection of the present invention.

[0043] When expressing a certain amount, concentration or other value or parameter in the form of a range, preferred range, or preferred upper and lower numerical limits, it should be understood that it is equivalent to specifically disclosing any range by combining any pair of upper range limits or preferred numerical values ​​with any lower range limit or preferred numerical value, without considering whether the range is specifically disclosed. Unless otherwise indicated, the numerical range values ​​listed herein include the endpoints of the range and all integers and fractions within the range.

[0044] Unless otherwise indicated, all percentages, parts, ratios, etc. herein are by weight.

[0045] This document provides general and / or specific descriptions of the materials and experimental methods used in the experiments. Unless otherwise specified, all experimental or testing methods are conventional methods. Materials and instruments used, unless the manufacturer is specified, are commercially available, conventional products and were prepared or used using conventional methods.

[0046] The test methods used in the following examples include:

[0047] The electrochemical performance was demonstrated by testing the main properties of each test sample separately; the device energy storage performance was tested using a CHI760E electrochemical workstation with a voltage window of 0.4-1.7 V. The main properties tested in this application include rate performance, constant current charge and discharge performance, and cycle performance.

[0048] Example 1

[0049] This embodiment provides a method for preparing 1,4,5,8-phenanthrene diquinone active substance, which comprises the following steps:

[0050] A1: Dissolve 1 part by weight of 5,8-dimethoxy-1,4-phenanthranaquinone in 75 parts by weight of acetonitrile solution, raise the temperature to 50° C. under stirring, and mix well to obtain a mixed solution;

[0051] A2: dissolving 2 parts by weight of ammonium cerium nitrate in water to form an oxidant solution;

[0052] A3: Rapidly add the ammonium cerium nitrate solution to the above mixed solution, stir and react at 50°C for 1 hour to obtain a reaction solution;

[0053] A4: Add distilled water to the reaction solution and extract with dichloromethane three times;

[0054] A5: The organic phase after extraction is washed with distilled water, then with a saturated sodium chloride solution, and then dried with anhydrous sodium sulfate.

[0055] A6: The solvent was removed by distillation under reduced pressure at 40°C, and then dried in a vacuum drying oven at 60°C for 24 hours to obtain the product, which was the active substance 1,4,5,8-phenanthrene diquinone.

[0056] The product prepared by A6 was characterized by Fourier transform infrared spectroscopy. Figure 1 As shown in the figure, at 1655cm -1 The peak at is the stretching vibration peak of the carbonyl group (C=O), and the remaining peaks are the C=C and CH vibration peaks on the benzene ring, indicating that the synthesized 1,4,5,8-phenanthrene diquinone active substance has carbonyl and benzene ring structures.

[0057] At the same time, the product 1HNMR and 13 CNMR test further verified the chemical structure of the active substance product of 1,4,5,8-phenanthrene diquinone. Using deuterated chloroform as solvent, the results are as follows Figure 2 、 3 As shown in the figure, it can be seen that the 1,4,5,8-phenanthrene diquinone active material was analyzed by H NMR at 400 MHz, where the H spectrum peak shift values ​​δ were 8.44 (s, 2H), 7.22 (d, 2H) and 7.03 (d, 2H) ppm. The carbon spectrum peak shift values ​​δ were 183.58, 183.03, 140.92, 136.55, 136.52, 134.00 and 130.30 ppm, respectively. The above results indicate that the target product 1,4,5,8-phenanthrene diquinone active material has been successfully prepared.

[0058] The chemical structural formula of the 1,4,5,8-phenanthrene diquinone active substance prepared in this application is:

[0059]

[0060] Example 2

[0061] Based on Example 1, this example provides a method for preparing an organic cathode material containing 1,4,5,8-phenanthrene diquinone active substance, which comprises the following steps:

[0062] B1: 4 parts by weight of 1,4,5,8-phenanthrene diquinone active material and 3 parts by weight of graphite were mixed and uniformly ground for 4 hours, and then 1 part by weight of polytetrafluoroethylene solution was added to obtain a fluid paste slurry;

[0063] B2: The slurry prepared in step B1 was evenly coated on the titanium mesh current collector, with the coating area being 1 cm 2 , and placed in a vacuum drying oven at 60°C for 24 hours to obtain the organic cathode material to be assembled.

[0064] Example 3

[0065] Based on Example 1, this example provides a method for preparing an organic cathode material containing 1,4,5,8-phenanthrene diquinone active substance, which comprises the following steps:

[0066] B1: 6 parts by weight of 1,4,5,8-phenanthrene diquinone active material and 4 parts by weight of graphite were mixed and uniformly ground for 4 hours, and then 1 part by weight of polytetrafluoroethylene solution was added to obtain a fluid paste slurry;

[0067] B2: The slurry prepared in step B1 is evenly coated on the carbon cloth current collector, with the coating area being 1 cm 2 , and placed in a vacuum drying oven at 60°C for 24 hours to obtain the organic cathode material to be assembled.

[0068] Example 4

[0069] Based on Example 1, this example provides a method for preparing an organic cathode material containing 1,4,5,8-phenanthrene diquinone active substance, which comprises the following steps:

[0070] B1: 8 parts by weight of 1,4,5,8-phenanthrene diquinone active material and 5 parts by weight of graphite were mixed and uniformly ground for 4 hours, and then 1 part by weight of polytetrafluoroethylene solution was added to obtain a fluid paste slurry;

[0071] B2: The slurry prepared in step B1 was evenly coated on the stainless steel mesh current collector, with the coating area being 1 cm 2 , and placed in a vacuum drying oven at 60°C for 24 hours to obtain the organic cathode material to be assembled.

[0072] Example 5

[0073] Based on Example 1, this example provides a method for preparing an organic cathode material containing 1,4,5,8-phenanthrene diquinone active substance, which comprises the following steps:

[0074] B1: 6 parts by weight of 1,4,5,8-phenanthrene diquinone active material and 3 parts by weight of graphite were mixed and uniformly ground for 4 hours, and then 1 part by weight of polytetrafluoroethylene solution was added to obtain a fluid paste slurry;

[0075] B2: The slurry prepared in step B1 is evenly coated on the carbon cloth current collector, with the coating area being 1 cm 2 , and placed in a vacuum drying oven at 60°C for 24 hours to obtain the organic cathode material to be assembled.

[0076] Example 6

[0077] This embodiment takes Example 5 as an example to provide an aqueous zinc battery containing the organic positive electrode material prepared in Example 5, wherein the preparation method thereof comprises the following steps:

[0078] C1: The prepared organic cathode material is used as the positive electrode, and the metal zinc sheet with a purity of not less than 99.99% is used as the negative electrode;

[0079] C2: Use a Zn(CF3SO3)2 solution with a molar concentration of 3M as the electrolyte, arrange the positive and negative electrodes and place them in an electrolytic cell to assemble an aqueous zinc battery.

[0080] The present application tests the electrochemical performance of the aqueous zinc battery prepared in this embodiment using an electrochemical workstation, and the voltage window is 0.4-1.7V.

[0081] The constant current charge and discharge curve of the aqueous zinc battery electrode based on 1,4,5,8-phenanthrene diquinone active material is as follows Figure 4 As shown in the figure, it can be seen that the average discharge voltage of the 1,4,5,8-phenanthrene diquinone active material is 0.88V. According to the formula E=C m ×ΔV, the energy density is calculated to be 363Wh kg -1 , at a current density of 0.64 A g -1 , 2.56A g -1 , 5.13A g -1 , 10.26Ag -1 、20.51A g -1 、41.02A g -1 、64.10A g -1 When the capacity is 412.28mAh g -1 、352.99mAh g -1 、315.52mAh g -1 , 287.29mAh g -1 、251.37mAh g -1 、193.60mAh g -1 and 138.95mAh g -1 , through formula C theo =nF / 3.6Mw, the theoretical capacity is calculated to be 450.44mAh g -1 , we can know that the active site utilization rate C m / C theo As high as 92%, when the current density increases 100 times, the capacity is still 138.95mAh g -1 , indicating its excellent rate performance and large current charge and discharge performance.

[0082] In addition, the cycle life curve of the aqueous zinc battery electrode based on 1,4,5,8-phenanthrene diquinone active material is as follows Figure 5 As shown, at 5.13A g -1 After 1000 cycles at a current density of 222.11 mAh g -1 The specific capacity of the battery is as high as 71.62%, and the coulombic efficiency is still 100% after 1000 cycles. The above results show that it still has good electrochemical performance after multiple charge and discharge cycles.

[0083] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some or all of the technical features therein. These modifications or replacements do not deviate the essence of the corresponding technical solutions from the scope of the technical solutions of the embodiments of the present invention, and they should all be included in the scope of the claims and description of the present invention.

Claims

1. An aqueous zinc battery, characterized in that: The organic cathode material is prepared by the following method, which specifically comprises the following steps: B1: Mix 1,4,5,8-phenanthrene diquinone active material and graphite in a mass ratio of (4-8): (5-3): 1, grind them evenly, and then add polytetrafluoroethylene solution to obtain a fluid paste slurry; B2: The slurry is evenly coated on a current collector, and dried to obtain the organic positive electrode material.

2. The aqueous zinc battery according to claim 1, wherein: in, The aqueous zinc battery is obtained by the following assembly method, which specifically comprises the following steps: C1: the organic cathode material is used as the positive electrode, and metallic zinc is used as the negative electrode; C2: Arrange the positive electrode and the negative electrode and place them in an electrolytic cell to assemble a battery.

3. The aqueous zinc battery according to claim 2, wherein: The purity of the metallic zinc is ≥99.99%; the diaphragm material includes but is not limited to filter paper and glass fiber; the electrolyte includes but is not limited to ZnCl2, ZnSO4 or Zn(CF3SO3)2 aqueous solution, and the electrolyte concentration is 1-10 M.

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