A fast chemical self-charging battery based on cyclonaphthacene diquinone positive material and a preparation method thereof

Abstract

The application belongs to the technical field of electrochemical energy storage, and more particularly relates to a fast chemical self-charging battery based on a cyclotriphthalonitrile positive electrode material and a preparation method thereof. The fast chemical self-charging battery comprises a positive electrode, a negative electrode, an electrolyte and a separator; the positive electrode is obtained by mixing or compounding an electrochemically active carbonyl-containing organic material cyclotriphthalonitrile and a conductive agent. The conductive agent can improve the oxygen redox rate, reduce the oxygen reduction reaction overpotential, and then quickly oxidize the positive electrode active material to a high voltage state, thereby completing the self-charging process of the chemical battery in a short time and meeting the timeliness under insufficient conditions. The problems of long charging time and poor convenience of the current fast chemical self-charging battery are solved.

Description

Technical Field

[0001] This invention belongs to the field of electrochemical energy storage technology, and more specifically relates to a fast chemical self-charging battery based on cyclotrinaphthoquinone cathode material and its preparation method. Background Technology

[0002] With the rapid development of modern industry, the problem of energy shortage is becoming increasingly prominent. At the same time, an irrational energy structure has further exacerbated environmental degradation, seriously threatening human survival. However, the susceptibility of renewable energy to natural factors and other conditions limits its large-scale, efficient utilization. Therefore, attention is focused on advanced electrochemical energy storage devices with unique advantages, such as lithium-ion batteries, fuel cells, and supercapacitors. These new energy storage devices can improve the utilization rate of renewable resources while better meeting people's daily needs.

[0003] Zinc-air batteries, as a novel battery technology, originated in the mid-20th century. Their development can be traced back to the early 1950s, when scientists successfully assembled the first zinc-air battery using metallic zinc as the anode, carbon powder as the cathode, silver wire as the air electrode, and NH4Cl as the electrolyte. Since the last century, zinc-air batteries have been successfully commercialized, initially used in hearing aids due to their high safety and long lifespan. Currently, zinc-air batteries are gradually being applied to electric vehicles, seismic probes, and long-distance communication, among other fields.

[0004] With the continuous advancement of science and technology, the materials used in air electrodes are constantly being innovated. Today, commercially available air electrodes consist of a catalytic layer, a current collector layer, and a gas diffusion layer. The catalytic layer is located near the electrolyte, the current collector layer is in the middle, and the gas diffusion layer is near the air. During the reaction, air enters the catalytic layer through the gas diffusion layer to participate in the reaction.

[0005] Electrochemical reactions in traditional inorganic materials involve the insertion and extraction of guest cations into and out of the host lattice, accompanied by valence state changes of transition metal cations. In contrast, quinone compounds store charge through an ion coordination mechanism. The carbonyl group (C=O) is reduced in a redox reaction to produce a negatively charged oxygen anion, which is then coordinated by a guest cation in the electrolyte. This cation can be a proton (H). + or alkali metals (Li + Na + Zn 2+ During redox reactions, cations are released, and quinones return to their neutral state. More importantly, quinone electrodes are generally not limited by counterion selection, making them suitable for monovalent Li... + Na + K + and H+ Or divalent Zn 2+ Mg 2+ and Ca 2+ Even multi-valent Al 3+ All of these are attractive, making quinones and their derivatives promising candidates for electrodes in advanced electrochemical energy storage devices.

[0006] Therefore, how to provide a fast chemical self-charging battery based on cyclotrinaphthalenediquinone cathode material and its preparation method is a technical problem that urgently needs to be solved by those skilled in the art. Summary of the Invention

[0007] To overcome the shortcomings and deficiencies of existing technologies, this invention provides a fast chemical self-charging battery based on cyclotrinaphthalenediquinone cathode material and its preparation method, which solves the problems of long charging time and poor convenience of current fast chemical self-charging batteries.

[0008] To achieve the above objectives, the present invention adopts the following technical solution:

[0009] A fast chemical self-charging battery based on cyclotrinaphthalenediquinone cathode material, the fast chemical self-charging battery comprising: a positive electrode, a negative electrode, an electrolyte, and a separator; The positive electrode is obtained by mixing or combining the electrochemically active carbonyl-containing organic material cyclotrinaphthalene with a conductive agent.

[0010] Preferably, the composite is selected from one of coating, spraying, or electrodeposition.

[0011] Preferably, the molecular formula of the cyclotrinaphthoquinone is C 30 H 12 O6, with a molecular weight of 468.06, has the following structural formula: .

[0012] Preferably, the conductive agent is selected from one of Ketjen black, conductive carbon, graphene, and carbon nanotubes.

[0013] Preferably, the negative electrode is zinc metal; The diaphragm is selected from one of polypropylene, polyethylene, polyimide, filter paper, and glass fiber.

[0014] Preferably, the electrolyte is selected from one of zinc sulfate aqueous solution and zinc trifluoromethanesulfonate aqueous solution.

[0015] This invention also provides a method for preparing the above-mentioned fast chemical self-charging battery, comprising the following steps: (1) Mix 1,4-naphthoquinone, 1,4-naphthodiol and the first solvent evenly, stir under a protective atmosphere, filter and remove impurities with the second solvent; then dry to obtain cyclotrinaphthoquinone; (2) The cyclotrinaphthalene diquinone, conductive agent, binder and second solvent are mixed evenly to obtain a slurry. The slurry is coated on the current collector and dried to obtain the positive electrode. (3) Assemble the positive electrode, negative electrode, electrolyte and separator to obtain a fast chemical self-charging battery.

[0016] Preferably, in step (1), the amount of 1,4-naphthol used is 1-5% of the molar amount of 1,4-naphthoquinone; The protective atmosphere is nitrogen or argon, the temperature is 20-60℃, and the stirring time is 24-48h; The drying temperature is 80-100℃, and the time is 12-24h.

[0017] Preferably, both the first solvent and the second solvent are selected from pyridine, o-dichlorobenzene, N-methylpyrrolidone, and dichloromethane.

[0018] Preferably, in step (2), the adhesive is selected from polyvinylidene fluoride and polytetrafluoroethylene; The current collector is selected from one of carbon cloth, carbon paper, titanium foil, and titanium mesh.

[0019] Preferably, in step (2), the mass ratio of the cyclotrinaphthoquinone, the conductive agent, and the binder is 5-7:3-4:1.

[0020] As can be seen from the above technical solution, compared with the prior art, the present invention has the following beneficial effects: (1) The positive electrode material of the present invention is composed of active material and conductive agent. The conductive agent can increase the oxygen oxidation-reduction rate and reduce the overpotential of oxygen reduction reaction, thereby quickly oxidizing the positive electrode active material to a high voltage state and completing the self-charging process of the chemical battery in a short time, thus meeting the timeliness requirements under insufficient conditions.

[0021] (2) This invention uses quinone compounds as the positive electrode material. Quinone compounds are cyclic conjugated unsaturated diketones, and the quinone molecule contains a special structure of cyclohexadienide. Due to the rapid redox kinetics and stable structure of the quinone group, quinone compounds have great potential in achieving high-rate capability and long-term cycling stability.

[0022] (3) The cathode material of the present invention is applicable to a variety of batteries, such as lithium-ion batteries, zinc-ion batteries, sodium-ion batteries, hydrogen-ion batteries and hybrid-ion batteries. Attached Figure Description

[0023] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the provided drawings without creative effort.

[0024] Figure 1 This is a schematic diagram of the fast chemical self-charging battery of Example 2.

[0025] Figure 2 The cyclotrinaphthoquinone of Example 1 13 C solid NMR spectrum.

[0026] Figure 3 The first constant current charge-discharge curve of the aqueous zinc-ion battery in Example 1 at a current density of 5 A / g is shown.

[0027] Figure 4 The self-charge and discharge specific capacity curves of the fast chemical self-charging battery in Example 2 at a current density of 5 A / g are shown.

[0028] Figure 5 The image shows the time-voltage curve of the fast chemical self-charging battery in Example 2.

[0029] Figure 6 This is the multiple charge-discharge capacity curve of the fast chemical self-charging battery in Example 2.

[0030] Figure 7 The voltage recovery test curve is shown for the fast chemical self-charging battery in Example 2. Detailed Implementation

[0031] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0032] Example 1 1,4-Naphthoquinone, 1,4-naphthodiol (1,4-naphthodiol was used at 5% of the molar amount of 1,4-naphthoquinone), and pyridine were mixed thoroughly and stirred in nitrogen at 50°C for 24 h. After filtration, impurities were removed using N-methylpyrrolidone; then, the mixture was dried at 100°C for 24 h to obtain cyclotrinaphthoquinone. 13 C solid-state NMR spectrum as follows Figure 2As shown, cyclotrinaphthalene, conductive agent Ketjen black, binder polyvinylidene fluoride, and N-methylpyrrolidone were uniformly mixed to obtain a slurry (the mass ratio of cyclotrinaphthalene: conductive agent: binder was 6:3:1). The slurry was coated onto carbon paper and vacuum dried at 80°C for 8 h in a vacuum drying oven to obtain the positive electrode.

[0033] The molecular formula of the obtained cyclotrinaphthoquinone is C 30 H 12 O6, with a molecular weight of 468.06, has the following structural formula: .

[0034] Example 1 uses a CR2032 coin cell. The battery assembly sequence is as follows: negative electrode shell, negative electrode (14 mm zinc foil), separator (16 mm glass fiber filter membrane), electrolyte (100 μL 3M Zn(CF3SO3)2 solution or 2M ZnSO4 solution), positive electrode sheet, gasket, spring contact, and positive electrode shell. After assembly, the battery is heated to 75 kg·cm⁻¹. -2 The batteries were sealed for 10 seconds under a pressure of 7.35 MPa. After activation overnight at room temperature, electrochemical performance tests were performed. Two types of batteries, A and B, were tested.

[0035] A: Assemble a button-type zinc-ion battery using zinc foil as the negative electrode and 3M Zn(CF3SO3)2 solution as the electrolyte.

[0036] B: Assemble a button-type zinc-ion battery using zinc foil as the negative electrode and 2M ZnSO4 solution as the electrolyte.

[0037] Electrochemical performance tests were conducted on the aqueous zinc-ion battery of Example 1 using a Xinwei charge-discharge tester (RS-485). Figure 3 The first constant current charge-discharge curve of the aqueous zinc-ion battery in Example 1 at a current density of 5 A / g is shown. The test results show that with 3M Zn(CF3SO3)2 solution as the electrolyte, the zinc-ion battery has a discharge specific capacity of 275 mAh / g; with 2M ZnSO4 solution as the electrolyte, the discharge specific capacity is 100 mAh / g.

[0038] Example 2 The cyclotrinaphthoquinone obtained in Example 1, the conductive agent Ketjen black, the binder polyvinylidene fluoride, and N-methylpyrrolidone were uniformly mixed to obtain a slurry (the mass ratio of cyclotrinaphthoquinone: conductive agent: binder was 6:3:1). The slurry was coated onto carbon paper and vacuum dried at 80°C for 8 h in a vacuum drying oven to obtain the positive electrode.

[0039] Example 2 used a CR2032 coin cell with an openable positive electrode casing. A commercially available porous hydrophobic membrane was used to seal the positive electrode casing, allowing air permeability while preventing electrolyte evaporation. Zinc foil was used as the negative electrode, and 100 μL of 3M Zn(CF3SO3)2 solution was used as the electrolyte. Other experimental conditions were the same as in Example 1. A fast chemical self-charging battery was assembled.

[0040] Figure 1 This is a schematic diagram of the fast chemical self-charging battery of Example 2.

[0041] Electrochemical performance tests were performed on the fast chemical self-charging battery of Example 2. Figure 4 This is the self-charge and discharge specific capacity curve of the fast chemical self-charging battery in Example 2 at a current density of 5 A / g. Figure 4 Test results show that at a current density of 5 A / g, the first-cycle discharge specific capacity of the fast chemical self-charging battery reaches as high as 330 mAh / g. Compared with traditional assembly methods, the capacity of the fast chemical self-charging battery is not reduced due to the influence of the positive electrode shell.

[0042] The self-charging time-voltage curve of the fast chemical self-charging battery in Example 2 was tested. Experimental procedure: After the battery discharged, it was placed in an open circuit state, making it an open system. At this time, cyclotrinaphthalene diquinone lost electrons in a short time, released zinc ions, and inserted trifluoromethanesulfonate ions, restoring its charging state. Figure 5 The image shows the time-voltage curve of the fast chemical self-charging battery in Example 2. Figure 5 Test results show that the voltage can rise to 1.1 V after 2 hours of self-charging.

[0043] The self-charging and self-discharge capacity curves of the fast-charging chemical self-recharging battery of Example 2 were tested. Experimental procedure: After the battery discharged, it was self-charged. Program settings: discharge cut-off voltage 0.2 V, discharge current 5 A / g. The circuit was then disconnected, and the battery self-charged for 2 hours, with the voltage rising to approximately 1.1 V. The discharge test was then repeated under the same conditions, and this cycle was repeated. Test instrument: Xinwei charge-discharge tester (RS-485). Figure 6 This is the multiple charge-discharge capacity curve of the fast chemical self-charging battery in Example 2. Figure 6 The results showed that the cumulative discharge capacity of the fast chemical self-charging battery was as high as 2000 mAh / g or more.

[0044] Voltage recovery tests were conducted on the fast chemical self-charging battery of Example 2 in air and nitrogen. Figure 7The results show that the chemical self-recharging battery recovers 96% of its voltage within 2 hours in air, while it recovers 60% within 2 hours and 66% within 24 hours in nitrogen. This proves that the oxidation effect of air is indispensable and can rapidly charge the battery to over 95% within 2 hours.

[0045] The above test results show that during the self-charging process of this battery system, cyclotrinaphthalene can be rapidly oxidized to a high voltage state in an air atmosphere, restoring its charging state and thus completing the chemical self-charging process.

[0046] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A fast-charging chemical battery based on cyclotrinaphthalenediquinone cathode material, characterized in that, The fast chemical self-charging battery includes: a positive electrode, a negative electrode, an electrolyte, and a separator; The positive electrode is obtained by mixing or combining the electrochemically active carbonyl-containing organic material cyclotrinaphthalene with a conductive agent.

2. The fast chemical self-charging battery according to claim 1, characterized in that, The molecular formula of the cyclotrinaphthoquinone is C 30 H 12 O6, with a molecular weight of 468.06, has the following structural formula: 。 3. The fast chemical self-charging battery according to claim 1, characterized in that, The conductive agent is selected from one of Ketjen black, conductive carbon, graphene, and carbon nanotubes.

4. The fast chemical self-charging battery according to claim 1, characterized in that, The negative electrode is zinc metal; The diaphragm is selected from one of polypropylene, polyethylene, polyimide, filter paper, and glass fiber.

5. The fast chemical self-charging battery according to claim 1, characterized in that, The electrolyte is selected from either zinc sulfate aqueous solution or zinc trifluoromethanesulfonate aqueous solution.

6. The method for preparing a fast chemical self-charging battery according to any one of claims 1-5, characterized in that, Includes the following steps: (1) Mix 1,4-naphthoquinone, 1,4-naphthodiol and the first solvent evenly, stir under a protective atmosphere, filter and remove impurities with the second solvent; then dry to obtain cyclotrinaphthoquinone; (2) The cyclotrinaphthalene diquinone, conductive agent, binder and second solvent are mixed evenly to obtain a slurry. The slurry is coated on the current collector and dried to obtain the positive electrode. (3) Assemble the positive electrode, negative electrode, electrolyte and separator to obtain a fast chemical self-charging battery.

7. The method for preparing a fast chemical self-charging battery according to claim 6, characterized in that, In step (1), the amount of 1,4-naphthol used is 1-5% of the molar amount of 1,4-naphthoquinone; The protective atmosphere is nitrogen or argon, the temperature is 20-60℃, and the stirring time is 24-48h; The drying temperature is 80-100℃, and the time is 12-24h.

8. The method for preparing a fast chemical self-charging battery according to claim 6, characterized in that, The first solvent and the second solvent are both selected from pyridine, o-dichlorobenzene, N-methylpyrrolidone, and dichloromethane.

9. The method for preparing a fast chemical self-charging battery according to claim 6, characterized in that, In step (2), the adhesive is selected from polyvinylidene fluoride and polytetrafluoroethylene; The current collector is selected from one of carbon cloth, carbon paper, titanium foil, and titanium mesh.

10. The method for preparing a fast chemical self-charging battery according to claim 6, characterized in that, In step (2), the mass ratio of the cyclotrinaphthoquinone, conductive agent, and binder is 5-7:3-4:1.

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