Superconducting graphene conductive agent, preparation method thereof and alkaline zinc-manganese battery

Abstract

The invention provides a superconducting graphene conductive agent and a preparation method thereof and an alkaline zinc-manganese battery, the superconducting graphene conductive agent comprises carbon black, carbon nanotubes, graphene and a solvent, the carbon black is dispersed by a micromolecular dispersant, the carbon nanotubes are covalently functionalized, the graphene is dispersed by a macromolecular dispersant, and the solvent is covalently functionalized. And the specific surface areas of the carbon black, the carbon nanotubes and the graphene are sequentially increased to form a gradient, so that a multi-dimensional three-dimensional synergistic efficient conductive network is constructed. According to the conductive agent, a multi-dimensional, three-dimensional and stable efficient conductive network is constructed by using carbon material gradients with different structures, different specific surface areas and different dosage proportions, and meanwhile, a dispersing agent with a corresponding size or functionalization is selected according to the characteristics of the carbon material, so that the problem that the carbon material is difficult to uniformly disperse in composite use is effectively solved. The alkaline zinc-manganese battery using the conductive agent has excellent rate capability and long high and low temperature service life.

Description

Technical Field

[0001] This invention relates to the field of battery technology, specifically to a superconducting graphene conductive agent, its preparation method, and an alkaline zinc-manganese battery. Background Technology

[0002] Alkali manganese batteries are characterized by high discharge power, long shelf life, ease of use, and high cost-effectiveness, making them a dominant type of primary battery. As the application of alkaline manganese batteries becomes increasingly widespread, higher demands are being placed on their performance at high power levels and their long lifespan in various temperature environments. Therefore, it is necessary to optimize the materials, formulations, and structural components used in alkaline manganese batteries to maximize the electrical performance of the electrode materials. In particular, it is crucial to reduce the battery's internal resistance, minimize electrode passivation during discharge, and improve the stability of the electrode structure to ensure a longer service life for alkaline manganese batteries.

[0003] For alkaline manganese batteries, conductive agents are used during electrode fabrication to increase the electronic conductivity between active materials and between active materials and current collectors. This ensures the formation of a conductive network on the surface of the active materials, accelerating electron transport and giving alkaline manganese batteries excellent discharge characteristics. Currently used conductive agents are mostly based on carbon-based materials (such as conductive carbon black, carbon nanotubes, graphene, etc.), and are mostly used in single-structure applications. These still have path defects in electron transport, which is not conducive to the battery's use in high-current discharge and relatively harsh temperature environments. Even if carbon-based materials are used to compensate for the defects of single structures, it is still difficult to avoid poor dispersion of the conductive agent, which is very detrimental to the conductive agent achieving better conductivity. Summary of the Invention

[0004] The technical problem to be solved by this invention is to provide a superconducting graphene conductive agent and its preparation method, as well as an alkaline zinc-manganese battery. By utilizing a gradient of carbon materials with different structures, specific surface areas, and dosage ratios, a multidimensional, three-dimensional, and stable high-efficiency conductive network is constructed. At the same time, the problem of uniform dispersion of carbon materials is effectively solved by selecting dispersants or functionalizations of appropriate sizes according to the different structures and specific surface areas of the carbon materials.

[0005] In a first aspect, the present invention provides a superconducting graphene conductive agent for alkaline zinc-manganese batteries, comprising carbon black, carbon nanotubes, graphene, and a solvent. The carbon black is carbon black dispersed by a small molecule dispersant; The carbon nanotubes are covalently functionalized carbon nanotubes; The graphene is graphene dispersed by a macromolecular dispersant. Furthermore, the specific surface areas of the carbon black, carbon nanotubes, and graphene increase sequentially to form a gradient, thereby constructing a multi-dimensional, three-dimensional, synergistic, and highly efficient conductive network.

[0006] Furthermore, the specific surface area of ​​the carbon black is 50-300 m². 2 / g; the specific surface area of ​​the carbon nanotubes is 400-800m². 2 / g; the specific surface area of ​​the graphene is 1000-1500m². 2 / g; The composite structure is as follows: the carbon black fills the tiny gaps in the conductive agent based on its own zero-dimensional point structure, establishing primary point contact; the carbon nanotube, based on its own one-dimensional linear structure, serves as a long-range line connecting the conductive agent to form a long-range conductive bridge, establishing a tough framework for long-distance bridging and penetration; the graphene, based on its own two-dimensional surface structure, provides a broadband conductive plane, establishes an intrinsic conductive pathway, and encapsulates and connects the active material.

[0007] Furthermore, the carbon nanotubes are selected from one of carboxylated carbon nanotubes, hydroxylated carbon nanotubes, and aminated carbon nanotubes.

[0008] Furthermore, the small molecule dispersant is selected from one of octylphenol polyoxyethylene ether, nonylphenol polyoxyethylene ether, sorbitan ester, polysorbate, glyceryl stearate, cocoyl diethanolamide, stearic acid, sodium dodecylbenzene sulfonate, and sodium dodecyl sulfate. The macromolecular dispersant is selected from one of sodium carboxymethyl cellulose, polyvinylpyrrolidone, polyethylene oxide, polypropylene oxide, polyimide, sodium lignosulfonate, sodium polyacrylate, and styrene-maleic anhydride copolymer.

[0009] Furthermore, the solvent is selected from one of cyclohexanone, acetone, butanone, N-methylpyrrolidone, acetylacetone, methyl isobutyl ketone, isophorone, and dipropanol ketone.

[0010] Secondly, the present invention provides a method for preparing a superconducting graphene conductive agent, comprising the following steps: S1. First, dissolve and disperse the small molecule dispersant in a solvent using a sand mill. Then, add carbon black in batches to the sand mill for grinding and dispersion to obtain dispersion A. S2. First, dissolve and disperse the macromolecular dispersant in a solvent using a sand mill, then add the graphene in batches to the sand mill for grinding and dispersion to obtain dispersion B. S3. Dispersion A, dispersion B and covalently functionalized carbon nanotubes are added to a high-speed shear machine in a certain proportion and dispersed evenly. The solid content is adjusted with solvent to obtain superconducting graphene conductive agent. The specific surface areas of the carbon black, carbon nanotubes, and graphene increase sequentially to form a gradient, thereby enabling the superconducting graphene conductive agent to construct a multi-dimensional, three-dimensional, synergistic, and highly efficient conductive network.

[0011] Furthermore, the amount of the small molecule dispersant is 10-30% of the mass of the carbon black; The amount of the macromolecular dispersant is 1 to 5% of the mass of the graphite.

[0012] Furthermore, the mass ratio of the carbon black, covalently functionalized carbon nanotubes, and graphene is (60~80):(10~20):(10~20).

[0013] Furthermore, the solid content of the superconducting graphene conductive agent is 40% to 70%.

[0014] Furthermore, the specific surface area of ​​the carbon black is 50-300 m². 2 / g; the specific surface area of ​​the carbon nanotubes is 400-800m². 2 / g; the specific surface area of ​​the graphene is 1000-1500m². 2 / g; The composite structure is specifically: The carbon black fills the tiny voids in the conductive agent based on its own zero-dimensional point structure, thus establishing primary point contact. The carbon nanotubes, based on their own one-dimensional linear structure, act as long-range conductive agents to form long-range conductive bridges, establishing a tough framework for long-distance bridging and penetration. The graphene provides a broadband conductive plane based on its two-dimensional surface structure, establishes an intrinsic conductive pathway, and encapsulates and connects active materials.

[0015] Furthermore, the carbon nanotubes are selected from one of carboxylated carbon nanotubes, hydroxylated carbon nanotubes, and aminated carbon nanotubes.

[0016] Furthermore, the small molecule dispersant is selected from one of octylphenol polyoxyethylene ether, nonylphenol polyoxyethylene ether, sorbitan ester, polysorbate, glyceryl stearate, cocoyl diethanolamide, stearic acid, sodium dodecylbenzene sulfonate, and sodium dodecyl sulfate. The macromolecular dispersant is selected from one of sodium carboxymethyl cellulose, polyvinylpyrrolidone, polyethylene oxide, polypropylene oxide, polyimide, sodium lignosulfonate, sodium polyacrylate, and styrene-maleic anhydride copolymer. The solvent is selected from one of cyclohexanone, acetone, butanone, N-methylpyrrolidone, acetylacetone, methyl isobutyl ketone, isophorone, and dipropanol ketone.

[0017] Thirdly, the present invention provides an alkaline zinc-manganese battery, wherein the alkaline manganese battery comprises the superconducting graphene conductive agent described in the first aspect, or comprises a superconducting graphene conductive agent prepared by the method described in the second aspect.

[0018] The advantages of this invention are: (1) In this invention, the superconducting graphene conductive agent is selected by combining carbon black, carbon nanotubes and graphene as conductive agents. The zero-dimensional point structure carbon black is used as a filling base conductive agent to fill the small gaps and establish primary point contact. The one-dimensional linear structure carbon nanotubes are used as long-range line connecting conductive agents to play the role of long-range conductive bridge, establish long-distance bridging and penetration to form a tough skeleton. The two-dimensional surface structure graphene provides a broadband conductive plane, establishes intrinsic conductive pathways and encapsulates and connects active materials. The three are structurally synergistic and form a gradient in specific surface area, making the electron transport path shorter and faster, which can effectively reduce the polarization inside the battery and make the alkaline manganese battery have lower resistance and faster electrode reaction rate.

[0019] (2) In the superconducting graphene conductive agent of the present invention, carbon black with a small specific surface area is dispersed using a small molecule dispersant, while graphene with a large specific surface area is dispersed using a macromolecule dispersant. Carbon nanotubes, due to their large curvature of tubular structure, are prone to desorption and re-aggregation after dispersion by the dispersant. Therefore, surface-covalently functionalized carbon nanotubes are selected to ensure the long-term dispersion stability of the carbon material. In terms of carbon material dispersion, the structural characteristics of the material are fully considered, and dispersants of appropriate size or functionalization methods are selected to ensure that the prepared superconducting graphene conductive agent has good dispersion stability, ensuring that the electrode material exhibits excellent performance.

[0020] (3) The carbon materials with different structures, different specific surface areas and different dosage ratios selected in this invention are used to construct a multi-dimensional, three-dimensional and stable high-efficiency conductive network. The three work together to achieve the optimal conductivity of a single conductive agent with less total addition. This means that the dosage ratio of active materials in the electrode system can be further increased, which is more advantageous for preparing batteries with higher energy density and longer battery life.

[0021] (4) The superconducting graphene conductive agent prepared by the present invention is a conductive slurry that can be stored stably for a long time. When making battery electrodes, active materials and binders can be directly added to the conductive agent. Its solid content, viscosity and other parameters can be adjusted in a wide range according to requirements. It can adapt to various forming processes of electrodes, and the making of battery electrodes will become more convenient and efficient. Attached Figure Description

[0022] The present invention will be further described below with reference to the accompanying drawings and embodiments.

[0023] Figure 1This is a schematic diagram of the structure of the superconducting graphene conductive agent of the present invention. Detailed Implementation

[0024] The present invention provides a superconducting graphene conductive agent and its preparation method, as well as an alkaline zinc-manganese battery. By utilizing a gradient of carbon materials with different structures, specific surface areas, and dosage ratios, a multidimensional, three-dimensional, and stable high-efficiency conductive network is constructed. At the same time, the problem of uneven dispersion of carbon materials in composite applications is effectively solved by selecting dispersants or functionalizers of appropriate sizes according to the different structures and specific surface areas of the carbon materials.

[0025] The technical solution in this invention aims to solve the above-mentioned problems. The overall approach is as follows: Addressing the issues of uneven carbon material dispersion and electron transport path defects in single-structure conductive agents in alkaline zinc-manganese batteries, this invention selects three different carbon materials with varying dimensions: carbon black (zero-dimensional point structure) dispersed by a small-molecule dispersant, covalently functionalized carbon nanotubes (one-dimensional linear structure), and graphene (two-dimensional planar structure) dispersed by a macromolecular dispersant. Utilizing the gradient characteristic of their sequentially increasing specific surface areas, a multi-dimensional, three-dimensional, synergistic, and highly efficient conductive network is constructed. Simultaneously, appropriate dispersion methods or functionalization treatments are employed based on the structure and specific surface area characteristics of each carbon material to ensure dispersion stability. Ultimately, when the prepared superconducting graphene conductive agent is applied to alkaline zinc-manganese batteries, it effectively reduces battery internal resistance, improves discharge capacity at different temperatures and high-temperature storage capacity retention, and optimizes battery performance.

[0026] This invention provides a superconducting graphene conductive agent for alkaline zinc-manganese batteries, comprising carbon black, carbon nanotubes, graphene, and a solvent. The carbon black is carbon black dispersed by a small molecule dispersant. Due to the zero-dimensional point structure and relatively small specific surface area of ​​carbon black, a small molecule dispersant is selected to achieve uniform dispersion of carbon black and avoid agglomeration. The dispersed carbon black can effectively fill the small gaps inside the conductive agent, establish primary point contacts, and provide basic support for the multidimensional conductive network. At the same time, it ensures the dispersion stability of carbon black in the conductive agent and ensures that its function continues to be performed.

[0027] The carbon nanotubes are covalently functionalized carbon nanotubes. The functionalized carbon nanotubes can form long-range conductive bridges as one-dimensional linear structures, establish a tough skeleton for long-distance bridging and penetration, and enhance the long-range electron transport capability and structural stability of the conductive network. This can solve the problem of easy desorption and agglomeration of dispersants caused by the large curvature of the tubular structure of carbon nanotubes, and achieve long-term stable dispersion through covalent functionalization.

[0028] The graphene is graphene dispersed by a macromolecular dispersant; the dispersed graphene can provide a broadband conductive plane, establish intrinsic conductive pathways, effectively encapsulate and connect active materials, and improve the in-plane electron transport efficiency of the conductive network; at the same time, it ensures the dispersion stability of graphene in the conductive agent, utilizes the adsorption effect of the macromolecular dispersant to achieve uniform dispersion of graphene, prevents stacking and agglomeration, and thus adapts to the two-dimensional surface structure and large specific surface area characteristics of graphene.

[0029] Furthermore, the specific surface areas of the carbon black, carbon nanotubes, and graphene increase sequentially, forming a gradient that constructs a multi-dimensional, three-dimensional, synergistic, and highly efficient conductive network. This allows for the synergistic effect of the different dimensional structures and specific surface area gradients of zero-dimensional (carbon black), one-dimensional (carbon nanotubes), and two-dimensional (graphene), compensating for the electron transport path defects of single-structure conductive agents. The resulting multi-dimensional, three-dimensional conductive network shortens the electron transport path and increases its speed, effectively reducing battery internal resistance and polarization; improving the battery's discharge capacity at different temperatures (-20℃, 25℃, 60℃) and high-temperature storage capacity retention; and simultaneously reducing the total amount of conductive agent added, increasing the proportion of active material in the electrodes, which is beneficial for improving battery energy density.

[0030] The specific surface area of ​​the carbon black is 50-300 m². 2 / g; This range is suitable for the zero-dimensional point structure characteristics of carbon black: it can achieve stable dispersion through small molecule dispersants to avoid agglomeration; it can also effectively fill the small gaps inside the conductive agent to establish primary point contacts and provide basic support for the multi-dimensional conductive network; at the same time, it balances the specific surface area and dosage to avoid the increase in the amount of conductive agent due to excessive specific surface area, which would squeeze the proportion of active material in the electrode.

[0031] The specific surface area of ​​the carbon nanotubes is 400-800 m². 2 / g; This range, with a specific surface area between that of carbon black and graphene, is well-suited to their one-dimensional linear structure: it can serve as a long-range conductive bridge, connecting zero-dimensional carbon black and two-dimensional graphene to form a tough framework for long-distance bridging and penetration; it ensures long-range electron transport capability while avoiding dispersion difficulties or structural embrittlement caused by excessively high specific surface area, thus ensuring the stability of the conductive network. The specific surface area of ​​the graphene is 1000-1500 m². 2 / g; This range is suitable for its two-dimensional surface structure: it can provide a broadband conductive plane, establish intrinsic conductive pathways and effectively encapsulate and connect active substances; when combined with macromolecular dispersants, it can prevent stacking and aggregation, and maximize in-plane electron transport efficiency; at the same time, it forms a gradient with the former two, and strengthens the synergistic effect of the multidimensional structure.

[0032] The gradient combination of the specific surface area ranges of the three components achieves functional complementarity between zero-dimensional, one-dimensional, and two-dimensional structures, constructing a multi-dimensional, three-dimensional, synergistic, and highly efficient conductive network: making the electron transport path shorter and faster, effectively reducing the battery's internal resistance and polarization; improving the battery's discharge capacity at different temperatures such as -20℃, 25℃, and 60℃, as well as the high-temperature storage capacity retention rate; and also reducing the total amount of conductive agent added, increasing the proportion of active materials in the electrodes, which is beneficial for improving the battery's energy density.

[0033] like Figure 1 As shown, the composite structure is as follows: the carbon black 1 fills the tiny gaps in the conductive agent based on its own zero-dimensional point structure, establishing primary point contact; the carbon nanotube 2, based on its own one-dimensional linear structure, serves as a long-range line connecting the conductive agent to form a long-range conductive bridge, establishing a tough framework for long-distance bridging and penetration; the graphene 3, based on its own two-dimensional surface structure, provides a broadband conductive plane, establishes an intrinsic conductive pathway, and encapsulates and connects the active material 4.

[0034] The carbon nanotubes are selected from one of carboxylated carbon nanotubes, hydroxylated carbon nanotubes, and aminated carbon nanotubes.

[0035] The small molecule dispersant is selected from one of octylphenol polyoxyethylene ether, nonylphenol polyoxyethylene ether, sorbitan ester, polysorbate, glyceryl stearate, cocoyl diethanolamide, stearic acid, sodium dodecylbenzene sulfonate, and sodium dodecyl sulfate.

[0036] The macromolecular dispersant is selected from one of sodium carboxymethyl cellulose, polyvinylpyrrolidone, polyethylene oxide, polypropylene oxide, polyimide, sodium lignosulfonate, sodium polyacrylate, and styrene-maleic anhydride copolymer.

[0037] The solvent is selected from one of cyclohexanone, acetone, butanone, N-methylpyrrolidone, acetylacetone, methyl isobutyl ketone, isophorone, and dipropanol ketone. These solvents provide a suitable medium to dissolve the dispersant and a stable environment for the dispersion of carbon materials, ensuring the prepareability and storage stability of the conductive agent. The solid content and viscosity of the conductive agent can be adjusted to prepare a stable conductive slurry suitable for various electrode molding processes. Simultaneously, it ensures that the conductive agent does not agglomerate during long-term storage, facilitating the convenient and efficient fabrication of battery electrodes.

[0038] The method for preparing the conductive agent in this embodiment of the invention includes the following steps: S1. The small molecule dispersant is first dissolved and dispersed in a solvent using a sand mill. Then, carbon black is added to the sand mill in batches for grinding and dispersion to obtain dispersion A. The sand milling process ensures that the dispersant is fully dissolved and uniformly coats the carbon black particles, effectively inhibiting carbon black agglomeration. Adding carbon black in batches for grinding further improves the dispersion effect, ensuring that carbon black, as a zero-dimensional point structure material, can fill the small gaps in the conductive network and establish primary point contacts.

[0039] S2. First, the macromolecular dispersant is dissolved and dispersed in a solvent using a sand mill. Then, graphene is added in batches to the sand mill for grinding and dispersion to obtain dispersion B. The sand milling process allows the dispersant to be fully adsorbed on the surface of the graphene sheets, preventing the sheets from stacking and agglomerating. Adding graphene in batches for grinding ensures the integrity of its two-dimensional surface structure, which can subsequently provide a broadband conductive plane, establish intrinsic conductive pathways, and encapsulate and connect active materials.

[0040] S3. Dispersion A, dispersion B, and covalently functionalized carbon nanotubes are added sequentially to a high-speed shear mill in a specific ratio and dispersed uniformly. The solid content is adjusted with solvent to obtain the superconducting graphene conductive agent. The high-speed shearing process ensures that dispersion A (carbon black), dispersion B (graphene), and carbon nanotubes are uniformly mixed in a specific ratio. The solid content is adjusted to ensure that the conductive agent meets the requirements of different electrode forming processes, while also ensuring stable product storage and convenient use.

[0041] The amount of the small molecule dispersant is 10-30% of the mass of the carbon black. This dosage range ensures that the small molecule dispersant is fully adsorbed on the surface of the carbon black, inhibiting agglomeration through steric hindrance or electrostatic repulsion, achieving uniform dispersion, and balancing performance and cost. Too little dosage will lead to insufficient dispersion, and the carbon black agglomerates will not be able to fill the gaps in the conductive network; too much dosage may introduce excess organic components, reducing the overall conductivity of the conductive agent or increasing costs. The 10-30% range ensures the dispersion effect while avoiding excessive addition.

[0042] The amount of the macromolecular dispersant is 1-5% of the mass of the graphite. An amount of 1-5% is sufficient to cover the graphene surface and exert a dispersing effect. Excessive use of the macromolecular dispersant will cover the conductive surface of the graphene, reducing its in-plane electron transport efficiency; insufficient use will not effectively suppress stacking. The 1-5% range ensures dispersion stability while maximizing the retention of the graphene's conductivity.

[0043] The mass ratio of carbon black, covalently functionalized carbon nanotubes, and graphene is (60~80):(10~20):(10~20). Carbon black has a relatively low cost, and a high proportion can control the total cost. Carbon nanotubes and graphene are crucial for functionality but have higher costs. Adding them in appropriate amounts can leverage their advantages in long-range and in-plane conductivity while avoiding excessive costs. Furthermore, this ratio can reduce the total amount of conductive agent added, increase the proportion of active material in the electrode, and help improve the battery's energy density.

[0044] The superconducting graphene conductive agent has a solid content of 40% to 70%. Different molding processes (such as coating and calendering) have different requirements for slurry viscosity. A wide range of solid content allows for flexible viscosity adjustment to meet diverse process needs. Furthermore, this solid content range ensures the conductive agent maintains a stable slurry state, preventing agglomeration and stratification during long-term storage, facilitating transportation and use. Too low a solid content results in insufficient conductive particle concentration, affecting the construction of the conductive network; too high a content leads to an overly viscous slurry, making uniform dispersion difficult. The 40% to 70% range balances conductivity and ease of handling, ensuring the conductive agent has both good conductivity and ease of processing.

[0045] The main applications of the conductive agent in the embodiments of the present invention are: This conductive agent is applied to the production of alkaline zinc-manganese batteries, for example, in the production of the positive and negative electrodes of the LR6 alkaline zinc-manganese battery.

[0046] To better understand the above technical solutions, the following will provide a detailed explanation of the technical solutions in conjunction with the accompanying drawings and specific implementation methods. Example 1

[0047] The conductive agent in this embodiment includes carbon black, carbon nanotubes, graphene, and solvent.

[0048] The specific surface area of ​​the carbon black is 50 m². 2 / g; The specific surface area of ​​the carbon nanotubes is 400 m². 2 / g; The specific surface area of ​​the graphene is 1000 m². 2 / g.

[0049] The preparation method of the conductive agent in this embodiment is as follows: Ten parts of the small molecule dispersant octylphenol polyoxyethylene ether were first dissolved and dispersed in cyclohexanone using a sand mill, and then 100 parts of a specific surface area of ​​50 m² were... 2 / g of carbon black was added in batches to a sand mill for grinding and dispersion to obtain dispersion A; First, one part of the macromolecular dispersant polyvinylpyrrolidone was dissolved and dispersed in cyclohexanone using a sand mill. Then, 100 parts of a specific surface area of ​​1000 m² was added. 2 / g of graphene was added in batches to a sand mill for grinding and dispersion to obtain dispersion B; Dispersion A, dispersion B, and a specific surface area of ​​400 m² were mixed. 2 / g of carboxylated carbon nanotubes were added sequentially in a high-speed shear mill at a ratio of 60:20:20 and uniformly dispersed. The solid content was adjusted to 70% with cyclohexanone to obtain a superconducting graphene conductive agent.

[0050] Furthermore, this conductive agent was applied to the fabrication of the positive electrode of an alkaline zinc-manganese battery, model LR6. Example 2

[0051] The conductive agent in this embodiment includes carbon black, carbon nanotubes, graphene, and solvent.

[0052] The specific surface area of ​​the carbon black is 300 m². 2 / g; The specific surface area of ​​the carbon nanotubes is 800 m². 2 / g; The specific surface area of ​​the graphene is 1500 m². 2 / g.

[0053] The preparation method of the conductive agent in this embodiment is as follows: Using a sand mill, 30 parts of the small molecule dispersant sorbitan ester were first dissolved and dispersed in methyl ethyl ketone (MEK), and then 100 parts of a specific surface area of ​​300 m² were... 2 / g of carbon black was added in batches to a sand mill for grinding and dispersion to obtain dispersion A; Five parts of the macromolecular dispersant polyethylene oxide were first dissolved and dispersed in butanone using a sand mill. Then, 100 parts of a specific surface area of ​​1500 m² were... 2 / g of graphene was added in batches to a sand mill for grinding and dispersion to obtain dispersion B; Dispersion A, dispersion B, and a specific surface area of ​​800 m² were mixed. 2 Hydroxylated carbon nanotubes of / g were added sequentially in a high-speed shear mill at a ratio of 80:10:10 and uniformly dispersed. The solid content was adjusted to 40% with methyl ethyl ketone to obtain a superconducting graphene conductive agent.

[0054] Furthermore, this conductive agent was applied to the fabrication of the negative electrode of an alkaline zinc-manganese battery, model LR6. Example 3

[0055] The conductive agent in this embodiment includes carbon black, carbon nanotubes, graphene, and solvent.

[0056] The specific surface area of ​​the carbon black is 200 m². 2 / g; The specific surface area of ​​the carbon nanotubes is 600 m². 2 / g; The specific surface area of ​​the graphene is 1200 m². 2 / g.

[0057] The preparation method of the conductive agent in this embodiment is as follows: Using a sand mill, 20 parts of sodium dodecylbenzenesulfonate, a small molecule dispersant, were first dissolved and dispersed in N-methylpyrrolidone. Then, 100 parts of a specific surface area of ​​200 m² was added. 2 / g of carbon black was added in batches to a sand mill for grinding and dispersion to obtain dispersion A; Three parts of sodium polyacrylate, a macromolecular dispersant, were first dissolved and dispersed in N-methylpyrrolidone using a sand mill. Then, 100 parts of a specific surface area of ​​1200 m² were... 2 / g of graphene was added in batches to a sand mill for grinding and dispersion to obtain dispersion B; Dispersion A, dispersion B, and a specific surface area of ​​600 m² were mixed. 2 / g of aminated carbon nanotubes were added sequentially in a high-speed shear mill at a ratio of 70:15:15 and uniformly dispersed. The solid content was adjusted to 55% with N-methylpyrrolidone to obtain a superconducting graphene conductive agent. Furthermore, this conductive agent was applied to the fabrication of the positive electrode of an alkaline zinc-manganese battery, model LR6. Example 4

[0058] The conductive agent in this embodiment includes carbon black, carbon nanotubes, graphene, and solvent.

[0059] The specific surface area of ​​the carbon black is 100 m². 2 / g; The specific surface area of ​​the carbon nanotubes is 700 m². 2 / g; The specific surface area of ​​the graphene is 1400 m². 2 / g.

[0060] The preparation method of the conductive agent in this embodiment is as follows: Ten parts of the small molecule dispersant glyceryl stearate were first dissolved and dispersed in isophorone using a sand mill, and then 100 parts of a specific surface area of ​​100 m² were... 2 / g of carbon black was added in batches to a sand mill for grinding and dispersion to obtain dispersion A; Four parts of sodium carboxymethyl cellulose, a macromolecular dispersant, were first dissolved and dispersed in isophorone using a sand mill. Then, 100 parts of a specific surface area of ​​1400 m² were... 2 / g of graphene was added in batches to a sand mill for grinding and dispersion to obtain dispersion B; Dispersion A, dispersion B, and a specific surface area of ​​700 m² were mixed. 2 / g of carboxylated carbon nanotubes were added sequentially in a high-speed shear mill at a ratio of 80:5:15 and uniformly dispersed. The solid content was adjusted to 60% with isophorone to obtain a superconducting graphene conductive agent.

[0061] Furthermore, this conductive agent was applied to the fabrication of the positive electrode of an alkaline zinc-manganese battery, model LR6. Example 5

[0062] The conductive agent in this embodiment includes carbon black, carbon nanotubes, graphene, and solvent.

[0063] The specific surface area of ​​the carbon black is 250 m². 2 / g; The specific surface area of ​​the carbon nanotubes is 500 m². 2 / g; The specific surface area of ​​the graphene is 1100 m². 2 / g.

[0064] The preparation method of the conductive agent in this embodiment is as follows: Using a sand mill, 25 parts of the small molecule dispersant nonylphenol polyoxyethylene ether were first dissolved and dispersed in acetylacetone, and then 100 parts of a specific surface area of ​​250 m² were... 2 / g of carbon black was added in batches to a sand mill for grinding and dispersion to obtain dispersion A; First, one part of the macromolecular dispersant sodium lignosulfonate was dissolved and dispersed in acetylacetone using a sand mill. Then, 100 parts of a specific surface area of ​​1100 m² was added. 2 / g of graphene was added in batches to a sand mill for grinding and dispersion to obtain dispersion B; Dispersion A, dispersion B, and a specific surface area of ​​500 m² were mixed. 2 Hydroxylated carbon nanotubes of / g were added sequentially in a high-speed shear mill at a ratio of 65:20:15 and uniformly dispersed. The solid content was adjusted to 50% with acetylacetone to obtain a superconducting graphene conductive agent.

[0065] Furthermore, this conductive agent was applied to the fabrication of the positive electrode of an alkaline zinc-manganese battery, model LR6.

[0066] Comparative Example 1 This comparative example provides a graphene conductive agent, and the preparation method of the graphene conductive agent is as follows: Five parts of the dispersant polyvinylpyrrolidone were first dissolved and dispersed in cyclohexanone using a sand mill. Then, 100 parts of graphene were added in batches to the sand mill for grinding and dispersion. The solid content was adjusted to 10% with cyclohexanone to obtain a graphene conductive agent.

[0067] Furthermore, this conductive agent was applied to the fabrication of the positive electrode of an alkaline zinc-manganese battery, model LR6.

[0068] Comparative Example 2 This comparative example provides a graphene conductive agent, and the preparation method of the graphene conductive agent is as follows: Carbon black, carbon nanotubes, and graphene were added sequentially to N-methylpyrrolidone in a ratio of 70:15:15 using a sand mill for grinding and dispersion. The solid content was adjusted to 30% using N-methylpyrrolidone to obtain a graphene conductive agent.

[0069] Comparative Example 3 This comparative example provides a graphene conductive agent, and the preparation method of the graphene conductive agent is as follows: Five parts of polyvinylpyrrolidone (PVP) dispersant were first dissolved and dispersed in N-methylpyrrolidone using a sand mill. Then, 70 parts of carbon black, 15 parts of carbon nanotubes, and 15 parts of graphene were added to the dispersant solution in sequence and ground and dispersed. The solid content was adjusted to 30% with N-methylpyrrolidone to obtain a graphene conductive agent.

[0070] Comparative Example 4 This comparative example provides a graphene conductive agent, and the preparation method of the graphene conductive agent is as follows: Using a sand mill, 30 parts of the dispersant sorbitan ester were first dissolved and dispersed in methyl ethyl ketone (MEK). Then, 70 parts of carbon black, 15 parts of carbon nanotubes, and 15 parts of graphene were added to the dispersant solution in sequence and ground and dispersed. The solid content was adjusted to 50% with MEK to obtain a graphene conductive agent.

[0071] The electrical performance of the alkaline zinc-manganese batteries prepared in Examples 1-5 and Comparative Examples 1-4 was tested. Ten batteries were taken from each test group, and the average value was taken as the test result. The results are shown in Table 1. The specific tests are as follows: Low temperature impedance value: First, discharge the battery to 50% SOC at 25℃ with a current of 500mA, then place the battery at -20℃ and apply a voltage of 10mV to the battery. Scan at a frequency of 1000Hz and record the low temperature impedance value. Battery discharge performance at different temperatures: The test temperatures were -20℃, 25℃ and 60℃, and the discharge was carried out under the conditions of discharge current and cutoff voltage of 1500mA and 0.8V, respectively. High-temperature storage performance: The battery was stored for 3 months in an environment below 60°C and with a relative humidity of less than 75%, and then discharged at a test temperature of 25°C with a discharge current of 1500mA and a cutoff voltage of 0.8V. The ratio of the discharge time obtained after high-temperature storage to the discharge time measured at 25°C was taken as the high-temperature storage capacity retention rate.

[0072] Table 1 Performance test results of alkaline zinc-manganese batteries

[0073] As shown in Table 1, the alkaline manganese batteries prepared using the superconducting graphene conductive agent from Examples 1-5 exhibit lower internal resistance at low temperatures compared to those prepared with ordinary graphene conductive agents. This indicates that the superconducting graphene conductive agent in this invention fully leverages the multi-dimensional synergistic effect of carbon black, carbon nanotubes, and graphene in their structure. The gradient composition of their specific surface areas results in superior electron transport performance at low temperatures. Discharge tests at different temperatures demonstrate that the alkaline manganese batteries prepared with the superconducting graphene conductive agent of this invention exhibit higher capacity at various temperatures, significantly improving battery life. Furthermore, the alkaline manganese batteries of this invention also demonstrate excellent high-temperature storage capacity retention, indicating that the superconducting graphene conductive agent can be uniformly dispersed in the electrode system and construct a highly stable and efficient conductive network.

[0074] While specific embodiments of the present invention have been described above, those skilled in the art should understand that the specific embodiments described are merely illustrative and not intended to limit the scope of the present invention. Equivalent modifications and variations made by those skilled in the art in accordance with the spirit of the present invention should be covered within the scope of protection of the claims of the present invention.

Claims

1. A superconducting graphene conductive agent, characterized in that: Including carbon black, carbon nanotubes, graphene, and solvents; The carbon black is carbon black dispersed by a small molecule dispersant; The carbon nanotubes are covalently functionalized carbon nanotubes; The graphene is graphene dispersed by a macromolecular dispersant. Furthermore, the specific surface areas of the carbon black, carbon nanotubes, and graphene increase sequentially to form a gradient, thereby constructing a multi-dimensional, three-dimensional, synergistic, and highly efficient conductive network.

2. The superconducting graphene conductive agent as described in claim 1, characterized in that: The specific surface area of ​​the carbon black is 50-300 m². 2 / g; The specific surface area of ​​the carbon nanotubes is 400-800 m². 2 / g; The specific surface area of ​​the graphene is 1000-1500 m². 2 / g; The composite structure is specifically: The carbon black fills the tiny voids in the conductive agent based on its own zero-dimensional point structure, thus establishing primary point contact. The carbon nanotubes, based on their own one-dimensional linear structure, act as long-range conductive agents to form long-range conductive bridges, establishing a tough framework for long-distance bridging and penetration. The graphene provides a broadband conductive plane based on its two-dimensional surface structure, establishes an intrinsic conductive pathway, and encapsulates and connects active materials.

3. The superconducting graphene conductive agent as described in claim 1, characterized in that: The carbon nanotubes are selected from one of carboxylated carbon nanotubes, hydroxylated carbon nanotubes, and aminated carbon nanotubes.

4. The superconducting graphene conductive agent as described in claim 1, characterized in that: The small molecule dispersant is selected from one of the following: octylphenol polyoxyethylene ether, nonylphenol polyoxyethylene ether, sorbitan ester, polysorbate, glyceryl stearate, cocoyl diethanolamide, stearic acid, sodium dodecylbenzene sulfonate, and sodium dodecyl sulfate. The macromolecular dispersant is selected from one of sodium carboxymethyl cellulose, polyvinylpyrrolidone, polyethylene oxide, polypropylene oxide, polyimide, sodium lignosulfonate, sodium polyacrylate, and styrene-maleic anhydride copolymer.

5. The superconducting graphene conductive agent as described in claim 1, characterized in that: The solvent is selected from one of cyclohexanone, acetone, butanone, N-methylpyrrolidone, acetylacetone, methyl isobutyl ketone, isophorone, and dipropanol ketone.

6. A method for preparing a superconducting graphene conductive agent, characterized in that: Includes the following steps: S1. First, dissolve and disperse the small molecule dispersant in a solvent using a sand mill. Then, add carbon black in batches to the sand mill for grinding and dispersion to obtain dispersion A. S2. First, dissolve and disperse the macromolecular dispersant in a solvent using a sand mill, then add the graphene in batches to the sand mill for grinding and dispersion to obtain dispersion B. S3. Dispersion A, dispersion B and covalently functionalized carbon nanotubes are added to a high-speed shear machine in a certain proportion and dispersed evenly. The solid content is adjusted with solvent to obtain superconducting graphene conductive agent. The specific surface areas of the carbon black, carbon nanotubes, and graphene increase sequentially to form a gradient, thereby enabling the superconducting graphene conductive agent to construct a multi-dimensional, three-dimensional, synergistic, and highly efficient conductive network.

7. The method as described in claim 6, characterized in that: The amount of the small molecule dispersant is 10-30% of the mass of the carbon black. The amount of the macromolecular dispersant is 1 to 5% of the mass of the graphite.

8. The method as described in claim 6, characterized in that: The mass ratio of carbon black, covalently functionalized carbon nanotubes and graphene is (60~80):(10~20):(10~20).

9. The method as described in claim 6, characterized in that: The solid content of the superconducting graphene conductive agent is 40%~70%.

10. The method as described in claim 6, characterized in that: The specific surface area of ​​the carbon black is 50-300 m². 2 / g; The specific surface area of ​​the carbon nanotubes is 400-800 m². 2 / g; The specific surface area of ​​the graphene is 1000-1500 m². 2 / g; The composite structure is specifically: The carbon black fills the tiny voids in the conductive agent based on its own zero-dimensional point structure, thus establishing primary point contact. The carbon nanotubes, based on their own one-dimensional linear structure, act as long-range conductive agents to form long-range conductive bridges, establishing a tough framework for long-distance bridging and penetration. The graphene provides a broadband conductive plane based on its two-dimensional surface structure, establishes an intrinsic conductive pathway, and encapsulates and connects active materials.

11. The method as described in claim 6, characterized in that: The carbon nanotubes are selected from one of carboxylated carbon nanotubes, hydroxylated carbon nanotubes, and aminated carbon nanotubes.

12. The method as described in claim 6, characterized in that: The small molecule dispersant is selected from one of the following: octylphenol polyoxyethylene ether, nonylphenol polyoxyethylene ether, sorbitan ester, polysorbate, glyceryl stearate, cocoyl diethanolamide, stearic acid, sodium dodecylbenzene sulfonate, and sodium dodecyl sulfate. The macromolecular dispersant is selected from one of sodium carboxymethyl cellulose, polyvinylpyrrolidone, polyethylene oxide, polypropylene oxide, polyimide, sodium lignosulfonate, sodium polyacrylate, and styrene-maleic anhydride copolymer. The solvent is selected from one of cyclohexanone, acetone, butanone, N-methylpyrrolidone, acetylacetone, methyl isobutyl ketone, isophorone, and dipropanol ketone.

13. An alkaline zinc-manganese battery, characterized in that: The alkaline manganese battery includes the superconducting graphene conductive agent according to any one of claims 1-5, or includes the superconducting graphene conductive agent prepared by the method according to any one of claims 6-12.

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