Bipolar organic electrode material and preparation method and application thereof

Abstract

The invention belongs to the technical field of electrochemical power supplies, and particularly relates to a bipolar organic electrode material and a preparation method and application thereof. The molecular structure of the tetraamino copper phthalocyanine has n-type (C = N) and p-type (-NH2) redox active centers at the same time, and positive ions and negative ions can be reversibly stored. The preparation method comprises the following steps: taking 4-nitrophthalonitrile and copper chloride as raw materials, cyclizing under the action of a catalyst to synthesize copper tetranitro phthalocyanine, and then converting nitro into amino through reduction reaction to obtain a target product. When the copper tetraamino phthalocyanine serving as the bipolar positive electrode material is applied to the aqueous zinc battery, high working voltage (-1.02 V vs. Zn / Zn < 2 + >) and relatively high specific capacity (137 mAh g <-1 >) are shown. In addition, the inherent planar large conjugate structure effectively inhibits dissolution in electrolyte, and endows the battery with excellent rate capability and long cycle stability. The material is simple in synthetic route and relatively low in cost, and has a wide application prospect in high-performance and low-cost aqueous zinc batteries.

Description

Technical Field

[0001] This invention belongs to the field of electrochemical power source technology, specifically relating to a bipolar organic electrode material, its preparation method, and its application. Background Technology

[0002] Developing efficient, low-cost, and sustainable energy storage technologies is crucial for addressing current energy and environmental challenges. Among numerous candidate solutions, aqueous zinc batteries stand out due to their high theoretical capacity (820 mAh g⁻¹) achieved by their zinc metal anode. -1 Zn has attracted much attention due to its advantages such as low redox potential (-0.76 V vs. SHE), abundant water resources, and intrinsic safety. To date, research has largely focused on inorganic cathode materials such as manganese-based, vanadium-based oxides, and Prussian blue analogues. However, Zn... 2+ The high charge-to-radius ratio of ions and their slow diffusion kinetics in inorganic lattices often lead to irreversible structural collapse and capacity decay in these materials during cycling, limiting their large-scale applications.

[0003] Compared to inorganic materials, organic electrode materials exhibit enormous application potential due to their abundant raw material sources, strong structural designability, and environmental friendliness. Based on energy storage mechanisms, organic cathode materials can be classified into n-type, p-type, and bipolar types. n-type materials (such as carbonyl and imine compounds) accept electrons through reduction reactions and react with Zn in the electrolyte. 2+ H + Isocation coordination for energy storage typically exhibits high specific capacity, but with a lower operating voltage (typically <0.8 V vs. Zn / Zn). 2+ The limited energy density and the easy solubility of small molecule materials in the electrolyte lead to poor cycle stability. Conversely, p-type materials (such as triphenylamine and phenothiazine derivatives) lose electrons through oxidation and react with ClO4. - CF3SO3 - Anion binding typically results in higher operating voltages and faster kinetics, but its limited active sites lead to generally lower specific capacities.

[0004] To synergize the high capacity of n-type materials with the high voltage of p-type materials, bipolar organic materials have emerged. These materials integrate electron acceptors (n-type sites) and electron donors (p-type sites) within the same molecular framework, enabling reversible storage of anions and cations, thus potentially overcoming the performance bottleneck of monopolar materials. However, currently reported bipolar organic materials still face several challenges: firstly, their redox active unit density is limited, and each active group typically undergoes only a single-electron reaction, leaving room for improvement in capacity and energy density; secondly, their molecular design and synthesis are highly complex; and thirdly, their long-cycle stability, especially at high rates, still needs further improvement. To address these issues, developing a bipolar organic electrode material that is easy to synthesize, structurally stable, and possesses excellent electrochemical performance is crucial for advancing the development of aqueous zinc batteries. Summary of the Invention

[0005] In view of this, the purpose of this invention is to at least partially solve one of the technical problems in the related art. To this end, it provides the application of tetraaminophthalocyanine copper in the preparation of battery slurries, electrode materials, or electrodes, particularly as a positive electrode material in aqueous zinc batteries, exhibiting excellent specific capacity, high operating voltage, and long cycle life. Tetraaminophthalocyanine copper has a well-defined molecular structure and abundant redox active sites, enabling it to simultaneously and reversibly store both anions and cations, possessing both high capacity and high operating voltage. Another object of this invention is to provide a battery slurry containing tetraaminophthalocyanine copper. A further object of this invention is to provide a method for preparing the aforementioned battery slurry. Furthermore, this invention also provides an organic electrode containing the battery slurry and an aqueous zinc battery containing the organic electrode.

[0006] The objective of this invention is achieved through the following technical solution: The first aspect provides the application of tetraaminophthalocyanine copper in the preparation of battery slurries, electrode materials, or electrodes.

[0007] In some embodiments of the first aspect, the battery slurry, electrode material, or electrode is used in an aqueous zinc battery, an organic zinc-ion battery, or a zinc-air battery.

[0008] Secondly, a battery slurry is provided, comprising tetraaminophthalocyanine copper, a conductive agent, and a binder solution, with a mass ratio of (4~8):(5~1):1, for example, 8:5:1, 8:4:1, 8:3:1, 8:2:1, 8:1:1, 7:5:1, 7:4:1, 7:3:1, 7:2:1, 7:1:1, 6:5:1, 6:4:1, 6:3:1, 6:2:1, 6:1:1, 5:5:1, 5:4:1, 5:3:1, 5:2:1, 5:1:1, 4:5:1, 4:4:1, 4:3:1, 4:2:1, 4:1:1.

[0009] In some embodiments of the second aspect, the conductive agent includes, but is not limited to, one or more of superconducting carbon black, graphite, carbon nanotubes, graphene, silver nanoparticles, copper nanoparticles, polyaniline, polypyrrole, Ketjen black, and acetylene black.

[0010] In some embodiments of the second aspect, the adhesive includes, but is not limited to, one or more of polyvinylidene fluoride, polytetrafluoroethylene, sodium carboxymethyl cellulose, styrene-butadiene rubber, and polyacrylic acid.

[0011] In some embodiments of the second aspect, the solvent includes, but is not limited to, one or more of N-methylpyrrolidone, DMF, ethanol, and water.

[0012] Thirdly, a method for preparing the battery slurry described in the second aspect is provided, specifically: mixing tetraaminophthalocyanine copper with a conductive agent, grinding evenly, and then adding a binder solution to obtain the battery slurry.

[0013] Fourthly, an organic electrode is provided, the preparation method of which includes the following steps: The battery slurry described in the second aspect is uniformly coated onto the current collector, and the organic electrode is obtained after drying.

[0014] In some embodiments of the fourth aspect, the current collector includes, but is not limited to, titanium foil, nickel mesh, titanium mesh, stainless steel mesh, and carbon cloth.

[0015] In some embodiments of the fourth aspect, the drying is vacuum drying, the drying temperature is 50~80 ℃, and the drying time is 12~36 h.

[0016] Fifthly, an aqueous zinc battery is provided, which is assembled using the organic electrode described in the fourth aspect.

[0017] In some embodiments of the fifth aspect, the aqueous zinc battery is obtained by the following assembly method, specifically including the following steps: C1: The organic electrode is used as the positive electrode, and the zinc metal is used as the negative electrode; C2: After arranging the positive electrode and the negative electrode, place them in an electrolytic cell to assemble a battery.

[0018] In some embodiments of the fifth aspect, the zinc metal has a purity of ≥99.99%.

[0019] In some embodiments of the fifth aspect, the diaphragm material includes, but is not limited to, filter paper and glass fiber.

[0020] In some embodiments of the fifth aspect, the electrolyte includes, but is not limited to, an aqueous solution of ZnCl2, ZnSO4, or Zn(CF3SO3)2.

[0021] In some embodiments of the fifth aspect, the electrolyte concentration is 1~10 M.

[0022] The structural formula of tetraaminophthalocyanine copper is shown below:

[0023] The preparation method of tetraaminophthalocyanine copper includes the following steps: A1: 4-Nitrophthalonitrile and a copper source are thoroughly mixed in a certain proportion in the presence of an organic solvent and a catalyst to obtain a mixed solution; A2: Stir repeatedly during the process to remove oxygen, evacuate the mixture, and heat it in an inert atmosphere to react. A3: Pour the solution after the reaction in A2 into a certain volume of alcohol solution, stir, let stand, and then filter under reduced pressure to obtain a solid crude product. A4: The solid crude product was washed and dried to obtain tetranitrophthalocyanine copper intermediate; A5: The tetranitrophthalocyanine copper intermediate obtained above is reacted with a reducing agent in a solvent at a certain ratio by heating and stirring to carry out a reduction reaction to obtain a reaction solution; A6: Pour the reaction solution into a certain volume of deionized water, stir, let stand, and then filter under reduced pressure to obtain the target crude product. A7: Washing and drying the target crude product yields a dark green solid, which is tetraaminophthalocyanine copper.

[0024] Preferably, in step A1, the copper source is anhydrous copper chloride, copper acetate, or copper sulfate; the organic solvent is n-hexanol, pentanol, or cyclohexanol; the catalyst is 1,8-diazabicyclo[5.4.0]undec-7-ene; the molar ratio of 4-nitrophthalonitrile to the copper source is (3.5~4.5):1; the amount of organic solvent used is 2~7 mL per millimole of 4-nitrophthalonitrile; and the amount of catalyst used is 30%~40% of the molar amount of 4-nitrophthalonitrile. Preferably, in step A2, the inert atmosphere is nitrogen or argon; the heating temperature is 130~160 ℃, and the reaction time is 60~72 h; Preferably, in step A3, the alcohol solution is one or more of methanol, ethanol, or isopropanol; the volume of the alcohol solution is 80-300 mL. Preferably, in steps A4 and A7, the washing specifically involves washing with deionized water and anhydrous ethanol sequentially; the drying is vacuum drying at a temperature of 60~100 ℃ for 12~36 h. Preferably, in step A5, the reducing agent is sodium sulfide nonahydrate, sodium dithionite, or hydrazine hydrate; the solvent is N,N-dimethylformamide, dimethyl sulfoxide, or N-methylpyrrolidone; the molar ratio of the tetranitrophthalocyanine copper intermediate to the reducing agent is 1:(10~15); the heating temperature is 50~70 °C, and the reaction time is 1~3 h; Preferably, in step A6, the volume of the deionized water is 150~350 mL.

[0025] Compared with the prior art, the present invention has at least the following beneficial effects: 1) The tetraaminophthalocyanine copper molecule provided by this invention possesses both n-type (C=N) and p-type (-NH2) redox active centers, exhibiting typical bipolar characteristics, and can simultaneously and reversibly store Zn. 2+ The cations and anions in the electrolyte contribute synergistically to the capacity (137 mAh g). -1 And increase the operating voltage (up to 1.02 V vs. Zn / Zn) 2+ Therefore, it can be used as a bipolar organic electrode material.

[0026] 2) Tetraaminophthalocyanine copper possesses a large planar π-conjugated structure, and its molecules can form a stable solid-state conductivity mechanism through strong π-π stacking interactions, effectively inhibiting the dissolution of active materials in aqueous electrolytes. In some embodiments where tetraaminophthalocyanine copper is used as an electrode material in aqueous zinc batteries, at 1 A g... -1 Even after 10,000 cycles at a current density, the capacity retention rate is still 77%, demonstrating its excellent long-cycle stability.

[0027] 3) The tetraaminophthalocyanine copper provided by this invention can be obtained in only two steps. The synthesis route is simple, the reaction conditions are mild, the raw materials used are cheap and readily available, and the electrode preparation, electrolyte preparation and battery assembly are all carried out at room temperature and pressure. It is safe and pollution-free, which can further reduce the preparation cost and has good market application prospects.

[0028] Terminology Definition The term “and / or” should be understood to mean any one of the options or any combination of two or more of the options.

[0029] The term "battery paste" can also be referred to as "electrode paste". Attached Figure Description

[0030] To more clearly illustrate the specific embodiments of the present invention, the accompanying drawings used in the description of the specific embodiments or the prior art will be briefly introduced below.

[0031] Figure 1This is the infrared spectrum of the tetraaminophthalocyanine copper prepared in Example 1 of this invention; Figure 2 This is the UV-Vis absorption spectrum of the tetraaminophthalocyanine copper prepared in Example 1 of this invention; Figure 3 This is a constant current charge-discharge curve of the aqueous zinc battery electrode containing tetraaminophthalocyanine copper prepared in Example 6 of the present invention. Figure 4 This is a capacity-current density diagram of the aqueous zinc battery electrode containing tetraaminophthalocyanine copper prepared in Example 6 of this invention; Figure 5 This is a cycle life diagram of the aqueous zinc battery electrode containing tetraaminophthalocyanine copper prepared in Example 6 of the present invention. Detailed Implementation

[0032] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some, not all, of the embodiments of this invention. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0033] This invention provides a general and / or specific description of the materials and experimental methods used in the experiments. Unless otherwise specified, all experimental or testing methods are conventional methods; all materials and instruments used, unless otherwise specified, are commercially available conventional products prepared or used using conventional methods.

[0034] The test methods used in the following embodiments and comparative examples include: The electrochemical performance was demonstrated by testing the main properties of each test sample separately. The energy storage performance of the device was tested using a CHI760E electrochemical workstation within a voltage window of 0.5-1.5 V. The main performance parameters tested in this invention include rate performance, constant current charge-discharge performance, and cycle performance.

[0035] Example 1 This embodiment provides a method for preparing tetraaminophthalocyanine copper, which includes the following steps: A1: Weigh 0.865 g (5.0 mmol) of 4-nitrophthalonitrile and 0.175 g (1.25 mmol) of anhydrous copper chloride, and place them in a heat-resistant glass tube. Add 10 mL of n-hexanol and 0.25 mL of 1,8-diazabicyclo[5.4.0]undec-7-ene, and stir to mix thoroughly to obtain a mixture. A2: Stir repeatedly to remove oxygen, evacuate the mixture and fill it with nitrogen; place the reaction tube in a heat-collecting constant-temperature magnetic stirrer and heat it at 150 °C for 65 h under a nitrogen atmosphere.

[0036] A3: After naturally cooling to room temperature, pour the reaction solution into anhydrous ethanol, stir and let stand, then filter under reduced pressure to obtain the crude solid product. A4: The obtained solid was washed three times with anhydrous ethanol and deionized water, and then dried under vacuum at 60 °C for 24 h to obtain tetranitrophthalocyanine copper intermediate. A5: Take 0.70 g (0.92 mmol) of the prepared tetranitrophthalocyanine copper intermediate and 2.72 g (11.3 mmol) of sodium sulfide nonahydrate, put them into a heat-resistant glass tube, add 12 mL of N,N-dimethylformamide to obtain the reaction solution; heat the reaction to 60 °C and stir the reaction at this temperature for 1 h; A6: After the reaction is complete, cool to room temperature, pour the reaction solution into deionized water, stir for 1 hour, let stand overnight, and then filter under reduced pressure to obtain the target crude product. A7: The target crude product was washed repeatedly with large amounts of deionized water and anhydrous ethanol until the filtrate was clear; the obtained target crude product was vacuum dried at 60 °C for 24 h to obtain dark green tetraaminophthalocyanine copper.

[0037] The products prepared from A4 and A7 were characterized by Fourier transform infrared spectroscopy, and the results are as follows: Figure 1 As shown in the figure, the tetranitrophthalocyanine copper intermediate and the tetraaminophthalocyanine copper intermediate share some of the same characteristic peaks: 1100 and 742 cm⁻¹. -1 The absorption peak at 3338 cm⁻¹ is a characteristic peak of the phthalocyanine macrocycle, indicating successful phthalocyanine cyclization. -1 and 3190 cm -1 The characteristic peaks that appear are specific to the tensile vibration peaks of -NH2, and were originally located at 1520 and 1343 cm⁻¹. -1 The disappearance of the antisymmetric and symmetric stretching vibration peaks belonging to -NO2 indicates that the nitro group has been successfully reduced to an amino group. Furthermore, the unique stretching vibration absorption peak of the C=N bond appears at 1503 cm⁻¹. -1 These results demonstrate the successful synthesis of tetranitrophthalocyanine copper intermediate, tetraaminophthalocyanine copper. Furthermore, tetraaminophthalocyanine copper exhibits redox bipolarity, possessing dual C=N and -NH2 active sites.

[0038] The chemical structures of the tetranitrophthalocyanine copper intermediate and the tetraaminophthalocyanine copper were further verified by UV-Vis absorption spectrometry. Using N,N-dimethylformamide as the solvent, the results are as follows: Figure 2As shown in the figure, the characteristic B-band and Q-band are clearly visible. These characteristic peaks, located in the near-ultraviolet region (300~400 nm, B-band) and the visible light region (600~750 nm, Q-band), are the characteristic fingerprints of electronic transitions from the ground state (π) to the excited state (π*) in this delocalized macrocyclic system. The above results indicate that tetranitrophthalocyanine copper intermediate and tetraaminophthalocyanine copper have been successfully prepared.

[0039] The chemical structural formula of the tetraaminophthalocyanine copper prepared in this invention is as follows:

[0040] Example 2 Based on Example 1, this example provides a method for preparing an organic electrode containing tetraaminophthalocyanine copper, which includes the following steps: B1: Mix copper tetraaminophthalocyanine and graphite, grind them evenly for 4 hours, and then add polytetrafluoroethylene solution to obtain a free-flowing paste with a mass ratio of 4:3:1.

[0041] B2: The slurry prepared in step B1 is uniformly coated onto the titanium mesh current collector, with a coating area of ​​1 cm². 2 The organic electrode to be assembled was dried in a vacuum drying oven at 60 °C for 24 h.

[0042] Example 3 Based on Example 1, this example provides a method for preparing an organic electrode containing tetraaminophthalocyanine copper, which includes the following steps: B1: Mix copper tetraaminophthalocyanine and graphite, grind them evenly for 4 hours, and then add polytetrafluoroethylene solution to obtain a free-flowing paste with a mass ratio of 6:4:1.

[0043] B2: Uniformly coat the slurry prepared in step B1 onto the carbon cloth current collector, with a coating area of ​​1 cm². 2 The organic electrode to be assembled was dried in a vacuum drying oven at 60 °C for 24 h.

[0044] Example 4 Based on Example 1, this example provides a method for preparing an organic electrode containing tetraaminophthalocyanine copper, which includes the following steps: B1: Mix copper tetraaminophthalocyanine and graphite, grind them evenly for 4 hours, and then add polytetrafluoroethylene solution to obtain a free-flowing paste slurry with a mass ratio of 8:5:1.

[0045] B2: Uniformly coat the slurry prepared in step B1 onto the stainless steel mesh current collector, with a coating area of ​​1 cm². 2The organic electrode to be assembled was dried in a vacuum drying oven at 60 °C for 24 h.

[0046] Example 5 Based on Example 1, this example provides a method for preparing an organic electrode containing tetraaminophthalocyanine copper, which includes the following steps: B1: Mix copper tetraaminophthalocyanine and graphite, grind them evenly for 4 hours, and then add polytetrafluoroethylene solution to obtain a free-flowing paste with a mass ratio of 5:4:1.

[0047] B2: Uniformly coat the slurry prepared in step B1 onto the stainless steel mesh current collector, with a coating area of ​​1 cm². 2 The organic electrode to be assembled was dried in a vacuum drying oven at 60 °C for 24 h.

[0048] Example 6 This embodiment uses Example 5 as an example to provide an aqueous zinc battery containing the organic electrode prepared in Example 5. The preparation method includes the following steps: C1: The prepared organic electrode is used as the positive electrode, and a zinc sheet with a purity of not less than 99.99% is used as the negative electrode; C2: Using a 3 M Zn(CF3SO3)2 solution as the electrolyte, the positive and negative electrodes are arranged and placed in an electrolytic cell to assemble an aqueous zinc battery.

[0049] The electrochemical performance of the aqueous zinc battery prepared in this embodiment was tested using an electrochemical workstation with a voltage window of 0.5~1.5 V.

[0050] The constant current charge-discharge curve of the aqueous zinc battery electrode in this embodiment is as follows: Figure 3 As shown, from Figure 3 As can be seen, the average discharge voltage of the aqueous zinc battery electrode in this embodiment is 1.02 V, at a current density of 0.06 A g. -1 0.08 Ag -1 0.11 Ag -1 0.42 Ag -1 1.11 A g -1 4.17 A g -1 At that time, its capacity was 137.04 mAh g. -1 119.95 mAh g -1 108.73 mAh g -1 76.05 mAh g -1 59.97 mAh g -1 and 36.11 mAh g -1The maximum capacity is achieved at a current density of 0.06 A g. -1 137.04 mAh g -1 Furthermore, from Figure 4 As can be seen, when the current density increases tenfold, the discharge specific capacity still remains at 71.11 mAh g⁻¹. -1 With a capacity retention rate of 52%, it demonstrates good rate performance.

[0051] In addition, the cycle life curve of the aqueous zinc battery electrode in this embodiment is as follows: Figure 5 As shown, in 1 Ag -1 After 10,000 cycles at a current density, the capacity retention rate is as high as 77%, and the coulombic efficiency is still 100% after 10,000 cycles. These results indicate that the aqueous zinc battery of this embodiment still has good electrochemical performance after multiple charge and discharge cycles.

[0052] Comparative Example 1 Based on Example 1, the tetranitrophthalocyanine copper intermediate obtained therefrom was used as a constituent material of the organic electrode, and its structure is as follows:

[0053] The method for preparing the organic electrode includes the following steps: mixing copper tetranitrophthalocyanine and graphite, grinding uniformly for 4 hours, and then adding polytetrafluoroethylene solution to obtain a fluid paste with a mass ratio of 5:4:1; uniformly coating the prepared paste onto a carbon cloth current collector, with a coating area of ​​1 cm². 2 The material was dried in a vacuum drying oven at 60 °C for 24 h to obtain the organic electrode to be assembled. Other steps were the same as the aqueous zinc battery preparation method in Example 6. The voltage window was 0.6~1.5 V, and its discharge capacity was tested, with a maximum capacity of 1.06 A g. -1 At a current density of 67 mAh g -1 Compared to Example 6, the battery capacity is significantly reduced at the same current density.

[0054] Comparative Example 2 Based on Example 1, without adding a copper source (anhydrous copper chloride), tetraaminophthalocyanine can be obtained, with the following structure:

[0055] Tetraaminophthalocyanine was used to prepare an organic electrode. The preparation method of the organic electrode includes the following steps: Tetraaminophthalocyanine and graphite were mixed and ground uniformly for 4 hours, and then polytetrafluoroethylene solution was added to obtain a fluid paste with a mass ratio of 5:4:1; the prepared paste was uniformly coated onto a stainless steel mesh current collector, with a coating area of ​​1 cm². 2The organic electrode was dried in a vacuum drying oven at 60 °C for 24 h to obtain the assembly. Other steps were the same as those for the aqueous zinc battery preparation method in Example 6. The voltage window was 0.5~1.5 V, and its discharge capacity was tested, with a maximum capacity of 0.08 A g. -1 36mAh g at current density -1 Compared to Example 6, its battery capacity is significantly reduced, only 26% of the maximum capacity of Example 6.

[0056] Comparative Example 3 Based on Example 1, without adding a copper source (anhydrous copper chloride) and without performing a reduction reaction to convert the nitro group to an amino group, tetranitrophthalocyanine can be obtained, with the following structure:

[0057] Tetranitrophthalocyanine is used to prepare organic electrodes. The preparation method of the organic electrode includes the following steps: mixing tetranitrophthalocyanine-based organic electrode material and graphite, grinding uniformly for 4 h, and then adding polytetrafluoroethylene solution to obtain a fluid paste with a mass ratio of 5:4:1; uniformly coating the prepared paste onto a stainless steel mesh current collector with a coating area of ​​1 cm². 2 The organic electrode was dried in a vacuum drying oven at 60 °C for 24 h to obtain the assembly. Other steps were the same as those for the aqueous zinc battery preparation method in Example 6. The voltage window was 0.6–1.5 V, and its discharge capacity was tested, with a maximum capacity of 0.13 A g. -1 21 mAh g at current density -1 Compared to Example 6, its battery capacity is significantly reduced, only 15% of the maximum capacity of Example 6.

[0058] Comparative Example 4 Based on Example 1, by replacing the copper source (anhydrous copper chloride) with the cobalt source (anhydrous cobalt chloride), tetraaminophthalocyanine cobalt can be obtained, with the following structure:

[0059] Tetraaminophthalocyanine cobalt is used to prepare organic electrodes. The preparation method of the organic electrode includes the following steps: mixing tetraaminophthalocyanine cobalt-based organic electrode material and graphite, grinding uniformly for 4 h, and then adding polytetrafluoroethylene solution to obtain a fluid paste with a mass ratio of 5:4:1; uniformly coating the prepared paste onto carbon cloth fluid, with a coating area of ​​1 cm². 2 The organic electrode was dried in a vacuum drying oven at 60 °C for 24 h to obtain the assembly. Other steps were the same as those in Example 6 for preparing the aqueous zinc battery. The voltage window was 0.4–1.5 V, and its discharge capacity was tested, with a maximum capacity of 0.85 A g. -184 mAh g at current density -1 Compared to Example 6, its battery capacity is significantly reduced.

[0060] Comparative Example 5 Based on Example 1, by replacing the copper source (anhydrous copper chloride) with the nickel source (anhydrous nickel chloride), tetraaminophthalocyanine nickel can be obtained, with the following structure:

[0061] The preparation of organic electrodes using nickel tetraaminophthalocyanine (NTC) includes the following steps: mixing NTC-based organic electrode material and graphite, grinding uniformly for 4 hours, and then adding polytetrafluoroethylene (PTFE) solution to obtain a fluid paste with a mass ratio of 5:4:1; uniformly coating the prepared paste onto a carbon cloth fluid, with a coating area of ​​1 cm². 2 The organic electrode was dried in a vacuum drying oven at 60 °C for 24 h to obtain the assembly. Other steps were the same as those in Example 6 for preparing the aqueous zinc battery. The voltage window was 0.4–1.5 V, and its discharge capacity was tested, with a maximum capacity of 0.72 A g. -1 57 mAh g at current density -1 Compared to Example 6, its battery capacity is significantly reduced.

[0062] Example 7 Based on Example 1, the tetraaminophthalocyanine copper obtained therefrom was used as the constituent material of the organic electrode. The preparation method of the organic electrode includes the following steps: mixing the tetraaminophthalocyanine copper-based organic electrode material and graphite, grinding them uniformly for 4 h, and then adding polytetrafluoroethylene solution to obtain a fluid paste with a mass ratio of 6:3:1; uniformly coating the prepared paste onto a stainless steel mesh current collector, with a coating area of ​​1 cm². 2 The organic electrode was dried in a vacuum drying oven at 60 °C for 24 h to obtain the assembly. Other steps were the same as those in Example 6 for preparing the aqueous zinc battery. The discharge capacity was tested within a voltage window of 0.5–1.5 V, with a maximum capacity of 0.06 A g. -1 92 mAh g at current density -1 Compared to Example 6, the battery capacity is reduced, but still higher than all the comparative examples mentioned above. In summary, tetraaminophthalocyanine copper is a preferred bipolar organic electrode material for assembling aqueous zinc battery electrodes.

[0063] 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 or all of the technical features therein. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention, and they should all be covered within the scope of the claims and specification of the present invention.

Claims

1. Use of copper tetraaminophthalocyanine in the preparation of a battery slurry, an electrode material or an electrode.

2. Use according to claim 1, characterized in that, The battery slurry, the electrode material or the electrode is used in a water-based zinc battery, an organic zinc ion battery or a zinc-air battery.

3. A battery slurry, characterized by, The battery slurry comprises copper tetraaminophthalocyanine, a conductive agent and a binder solution, and the mass ratio of the three is (4-8) : (5-1) :

1.

4. The battery slurry of claim 3, wherein The conductive agent comprises one or more of super conductive carbon black, graphite, carbon nanotubes, graphene, silver nanoparticles, copper nanoparticles, polyaniline, polypyrrole, ketjen black, acetylene black, but not limited to; and / or The binder comprises one or more of polyvinylidene fluoride, polytetrafluoroethylene, sodium carboxymethyl cellulose, styrene butadiene rubber and polyacrylic acid, but not limited to; and / or The solvent comprises one or more of N-methyl pyrrolidone, DMF, ethanol and water, but not limited to.

5. A method of preparing a battery slurry as claimed in claim 3 or 4, characterized in that, The battery slurry is obtained by mixing copper tetraaminophthalocyanine with a conductive agent, grinding them uniformly and then adding a binder solution.

6. An organic electrode, characterized by, The preparation method comprises the following steps: The organic electrode is obtained by uniformly coating the battery slurry of claim 4 or 5 on a current collector and drying.

7. The organic electrode of claim 6, wherein The current collector comprises one or more of titanium foil, nickel mesh, titanium mesh, stainless steel mesh and carbon cloth, but not limited to; and / or The drying is vacuum drying, the drying temperature is 50-80 ℃, and the drying time is 12-36 h.

8. An aqueous zinc battery, characterized by, The organic electrode of claim 6 or 7 is used for assembly.

9. The water-based zinc battery of claim 8, wherein The water-based zinc battery is obtained by the following assembly method, and the specific steps comprise: C1: the organic electrode is used as a positive electrode, and metal zinc is used as a negative electrode; C2: the positive electrode and the negative electrode are arranged and then placed in an electrolyte to assemble a battery.

10. The water-based zinc battery of claim 9, wherein The purity of the metal zinc is ≥ 99.99%; and / or The separator material comprises one or more of filter paper and glass fiber, but not limited to; and / or The electrolyte comprises one or more of ZnCl2, ZnSO4 or Zn(CF3SO3)2 aqueous solution, but not limited to; and / or The concentration of the electrolyte is 1-10 M.

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