Ultra-high structure and high specific surface area carbon black based on high crystallinity and preparation method thereof, electrode slurry, and battery

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A carbon black material with ultra-high structure and high specific surface area is produced via controlled activation and etching, addressing the limitations of existing materials by enhancing conductivity and stability in batteries and fuel cells.

JP2025165411APending Publication Date: 2025-11-04JIAOZUO CITY HEXING CHEMICAL INDUSTRY CO LTD

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Patent Information

Application Number: JP2025070554
Authority / Receiving Office: JP · JP
Patent Type: Applications
Current Assignee / Owner
Priority Date: 2024-04-22
Filing Date: 2025-04-22
Publication Date: 2025-11-04

AI Technical Summary

Technical Problem

Existing carbon black materials used in batteries and fuel cells face challenges due to low crystallinity, poor structural stability, and limited specific surface area, which affect conductivity and durability under high temperatures and voltages.

Method used

A carbon black material with ultra-high structure and high specific surface area is produced through a method involving pretreatment with an oxidizing agent, followed by activation and etching at controlled temperatures, maintaining a high degree of crystallinity and avoiding structural collapse.

Benefits of technology

The resulting carbon black exhibits enhanced conductivity, improved compatibility with electrolytes, and superior liquid absorption and retention capabilities, ensuring stable catalyst support and extended battery life.

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Abstract

To provide a carbon black having high crystallinity, ultra-high structure, and high specific surface area, which, when used as a conductive agent or carrier, improves the conductivity of an electrode active material and compatibility with an electrolyte due to the high graphitization degree of the carbon black, and enhances the stability of the carrier material to ensure catalyst activity.SOLUTION: The present invention relates to the technical field of carbon black materials, and more particularly to an ultra-high structure and high specific surface area carbon black based on high crystallinity, a preparation method thereof, an electrode slurry, and a battery. The ultra-high structure and high specific surface area carbon black based on high crystallinity satisfies the following conditions: (1) a degree of crystallinity of 39% or higher; (2) a BET specific surface area ranging from 200 m2 / g to 763 m2 / g (3) an OAN ranging from 334 mL / 100 g to 548 mL / 100 g; and (4) an average primary particle diameter of 35 nm or less.SELECTED DRAWING: Figure 1

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Description

[Technical Field]

[0001] The present invention relates to the technical field of carbon black materials, and in particular to carbon black having an ultra-high structure and a high specific surface area based on high crystallinity, a method for producing the same, an electrode slurry, and a battery. [Background technology]

[0002] In recent years, carbon black has been widely used in battery applications such as lithium-ion secondary batteries and fuel cells. A typical lithium-ion secondary battery consists of a positive electrode, a negative electrode, a separator, and an electrolyte. Carbon black is used as a conductive agent to enhance the conductivity of the positive electrode active material. Therefore, carbon black must have a high structure, high crystallinity, and high dispersibility to achieve a rich conductive network and good intrinsic conductivity. Carbon black is used as a catalyst support in fuel cells, and support particles must have a high surface area to maximize reactant / catalyst contact and enhance catalytic efficiency. However, due to corrosion at high battery voltages and temperatures, the specific surface area of carbon black accounts for a large proportion of the specific surface area of the powder material, even at low loadings, posing major challenges to the durability and stability of commonly used carbon black supports.

[0003] Therefore, carbon black preferably has a high structure, a high specific surface area, and a high degree of graphitization. Furnace carbon black has a relatively high specific surface area, but the product has low crystallinity and poor long-term stability. Furthermore, because impurities in the raw materials are difficult to remove, carbon black products contain a large amount of impurities, further adversely affecting their long-term stability and application. To increase the specific surface area of carbon black, it is typically etched at temperatures between 500°C and 950°C using an oxidizing agent such as air, oxygen gas, ozone, or water vapor. However, the carbon black after oxidation has a low degree of crystallinity, necessitating further high-temperature graphitization. The graphitization temperature is approximately 2000°C to 3000°C, which consumes a lot of energy. However, as the degree of graphitization of carbon black increases during high-temperature heat treatment, the carbon black structure tends to collapse, resulting in a decrease in total (internal) surface area and a decrease in the carbon black's performance in terms of electrolyte adsorption and storage. Furthermore, the branched structure of carbon black breaks or dissociates after oxidative etching, resulting in a lack of significant improvement in the carbon black structure after etching.

[0004] The existing product, Ketjenblack, has a relatively high specific surface area and abundant branched morphology, enabling it to achieve high conductivity with a small amount added. It has been used in high-end applications such as high-performance batteries and has long been a market leader. However, Ketjenblack is produced using the oil furnace method, which results in low production temperatures and extensive exposure to oxygen, resulting in low crystallinity. The average particle size of Ketjenblack's primary particles is 40 nm, which is comparable to the particle size of commercially available SP (SUPER P-Li conductive carbon black) and acetylene carbon black. This means that the number of primary particles is the same for carbon black of the same mass. Furthermore, Ketjenblack products are difficult to produce, have low product yields, and are expensive to produce. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2023 / 147235 Summary of the Invention [Problem to be solved by the invention]

[0006] The present invention aims to provide a carbon black with an ultra-high structure and a large specific surface area based on high crystallinity, a method for producing the same, an electrode slurry, and a battery. The carbon black of the present invention does not require high-temperature secondary graphitization treatment and has high crystallinity, an ultra-high structure, and a large specific surface area, which can improve the electrical conductivity of materials and enhance their liquid absorption and retention capabilities. [Means for solving the problem]

[0007] In order to achieve the above object of the present invention, the present invention provides a carbon black having an ultra-high structure and a large specific surface area based on a high crystallinity, which satisfies the following characteristics: (1) The crystallinity is 39% or more. (2) BET specific surface area is 200-763m 2 / g. (3) OAN is 334 to 548 mL / 100 g. (4) The average particle size of the primary particles is 35 nm or less.

[0008] In a specific embodiment of the present invention, the crystallite size Lc of the carbon black is 20.03 Å to 25.17 Å.

[0009] In a specific embodiment of the present invention, the crystallite size La of the carbon black is 27.8 Å to 37.5 Å.

[0010] In a specific embodiment of the present invention, the lattice fringes of the primary particles of carbon black exhibit an irregular hat-like or ring-like shape.

[0011] In a specific embodiment of the present invention, the crystallinity of the carbon black is 39% to 46%.

[0012] In a specific embodiment of the present invention, the aggregate size D of the carbon black 50Furthermore, the aggregate size D of carbon black is 95 nm or less. 50 is 68 nm or more.

[0013] In a specific embodiment of the present invention, the average lattice spacing d(002) of the carbon black is 0.3534 nm or less, for example, 0.3479 nm to 0.3534 nm.

[0014] In a specific embodiment of the present invention, the average particle size of the primary particles of the carbon black is 25 nm to 35 nm.

[0015] In a specific embodiment of the present invention, the carbon black has an average pore diameter of 5.86 nm to 9.04 nm.

[0016] In a specific embodiment of the present invention, the carbon black has a pore volume of 2 nm to 50 nm in size measured by nitrogen adsorption / desorption of 0.3157 cm 3 / g~1.2061cm 3 / g.

[0017] In a specific embodiment of the present invention, the volume of pores having a size of 2 nm to 50 nm accounts for 84.6% to 93.8% of the total pore volume of the carbon black.

[0018] Another aspect of the present invention provides a method for producing any of the above carbon blacks, comprising the step of subjecting pretreated raw carbon black to an activation etching treatment, wherein the activation etching treatment includes the steps of heating the raw carbon black to a first activation temperature in a protective atmosphere and performing an activation treatment under the action of an activation gas, cooling the raw carbon black to a second activation temperature and performing an etching treatment under the action of an activation gas, and then lowering the temperature to room temperature in a protective atmosphere, wherein the pretreatment includes the steps of placing the raw carbon black in an aqueous solution containing an oxidant and treating it at 30°C to 150°C for 0.5 to 2 hours, followed by washing and drying, wherein the first activation temperature is 1100°C to 1500°C and the second activation temperature is 900°C to 1000°C, and wherein the raw carbon black has a degree of crystallinity of 44% or higher.

[0019] In a specific embodiment of the present invention, the BET specific surface area of the raw carbon black is 60 m 2 / g~150m 2 / g, and the raw carbon black is acetylene carbon black.

[0020] In a specific embodiment of the present invention, the activation gas comprises at least one of nitrogen dioxide, nitric oxide, CO2, CO, oxygen gas, ozone, and water vapor.

[0021] In a specific embodiment of the present invention, the activation treatment time at the first activation temperature is 10 minutes to 30 minutes.

[0022] In a specific embodiment of the present invention, the duration of the etching treatment at the second activation temperature is 30 to 70 minutes.

[0023] In a specific embodiment of the present invention, the temperature is lowered at a rate of 2°C / min to 4°C / min.

[0024] In a specific embodiment of the present invention, the temperature rise rate is 4°C / min to 6°C / min.

[0025] In a specific embodiment of the present invention, the oxidizing agent comprises at least one of hydrogen peroxide and an oxoacid, which further comprises at least one of nitric acid, sulfuric acid, hypochlorous acid, and perchloric acid.

[0026] Yet another aspect of the present invention provides an electrode slurry containing any of the above carbon blacks.

[0027] Yet another aspect of the present invention provides a secondary battery comprising a positive electrode, a negative electrode, an electrolyte, and a separator, wherein at least one of the positive electrode and the negative electrode is produced from any of the electrode slurries described above.

[0028] Yet another aspect of the present invention provides a fuel cell comprising a catalyst, the catalyst comprising a support and active catalyst particles supported on the support, the support comprising any of the carbon blacks described above. [Effects of the Invention]

[0029] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0030] (1) The carbon black of the present invention has high crystallinity, ultra-high structure, and a large specific surface area. When used as a conductive agent or carrier, the high graphitization of the carbon black improves the conductivity of the electrode active material and compatibility with the electrolyte, and enhances the stability of the carrier material, thereby ensuring catalytic activity. At the same time, the carbon black of the present invention has excellent liquid absorption and retention capabilities and catalyst support stability.

[0031] (2) The method for producing carbon black of the present invention uses carbon black having a certain degree of crystallinity as a raw material, and pretreats the carbon black with an oxidizing agent to first oxidize the carbon black, followed by subsequent activation and etching to form carbon black with an ultra-high structure and a large specific surface area while avoiding collapse. The resulting carbon black has both liquid absorption and retention capacity and excellent electrical conductivity. [Brief explanation of the drawings]

[0032] [Figure 1] FIG. 2 is a scanning electron microscope image of the carbon black obtained in Example 3 of the present invention. [Figure 2] 1A to 1C are transmission electron micrographs of the carbon black obtained in Example 3 of the present invention, where (a) to (c) are transmission electron micrographs taken at different amplification magnifications. [Figure 3] 1 shows Raman spectra of the carbon black obtained in Example 1 of the present invention. [Figure 4] 1 is a Raman spectrum of the carbon black obtained in Example 2 of the present invention. [Figure 5]1 is a Raman spectrum of the carbon black obtained in Example 3 of the present invention. [Figure 6] 1 is a Raman spectrum of raw material carbon black used in an example of the present invention. [Figure 7] 1 is a Raman spectrum of the carbon black of Comparative Example 1. [Figure 8] 1 is a Raman spectrum of the carbon black of Comparative Example 2. [Figure 9] 1 is a size distribution curve of carbon black aggregates obtained in Example 1 of the present invention. [Figure 10] 1 is a size distribution curve of carbon black aggregates obtained in Example 2 of the present invention. [Figure 11] 1 is a size distribution curve of carbon black aggregates obtained in Example 3 of the present invention. [Figure 12] 1 is an aggregate size distribution curve of raw carbon black used in the examples of the present invention. [Figure 13] 1 is a size distribution curve of carbon black aggregates of Comparative Example 1. [Figure 14] 1 is a size distribution curve of carbon black aggregates of Comparative Example 2. [Figure 15] 1 shows XRD (X-ray diffraction) patterns of carbon blacks and raw material carbon blacks in Examples 1 to 3 and Comparative Examples 1 and 2 of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0033] In order to more clearly describe the technical solutions in the embodiments of the present invention or the prior art, the following briefly describes the drawings necessary for describing the embodiments of the present invention or the prior art. Obviously, it should be understood that the drawings in the following description only show some embodiments of the present application, and those skilled in the art can obtain other related drawings based on these drawings without using inventive ability.

[0034] The following clearly and completely describes the technical solutions of the present invention with the aid of drawings and specific embodiments. The examples described below are only some examples for illustrating the present invention, are not all examples, and should not be considered as limiting the scope of the present invention. All other examples obtained by those skilled in the art based on the examples of the present invention without using their inventive abilities also fall within the scope of protection of the present invention. In the examples, where specific conditions are not specified, the experiments can be carried out under conventional conditions or under conditions recommended by the manufacturer. Where the manufacturer of the reagents or machines used is not specified, conventional products available on the market can be used.

[0035] When carbon black is used as a conductive agent in secondary batteries, it is required to build a rich conductive network, have good intrinsic conductivity, and have a certain liquid absorption and retention capacity. When carbon black is used as a catalyst support in fuel cells, it is required to have a high specific surface area and stability. To meet the above various performance requirements, multiple parameters of carbon black must simultaneously satisfy certain ranges. However, carbon black in the prior art has not been able to simultaneously satisfy these multiple performance requirements.

[0036] Based on this, one aspect of the present invention provides a carbon black having an ultra-high structure and a high specific surface area based on a high crystallinity, which satisfies the following characteristics: (1) The crystallinity is 39% or more. (2) BET specific surface area (Brunauer-Emmett-Teller specific surface area) is 200 m 2 / g~763m 2 / g. (3) The OAN (Oil Absorption Number) is 334 mL / 100 g to 548 mL / 100 g. (4) The average particle size of the primary particles is 35 nm or less. In this specification, the term "high structure" refers to a structure in which the interior of a carbon black granule has a large void structure and a large surface area. The term "ultra-high structure" refers to a structure in which the interior of a carbon black granule has a large void structure and a large surface area, which is not conventionally found in the above (2) and (3).

[0037] The carbon black of the present invention has high crystallinity, ultra-high structure, and a high specific surface area. When used as a conductive agent or carrier, the high graphitization of the carbon black improves the conductivity of the electrode active material and compatibility with the electrolyte, and enhances the stability of the carrier material, thereby ensuring catalyst activity. At the same time, the carbon black of the present invention has excellent liquid absorption and retention capabilities and catalyst support stability.

[0038] The degree of graphitization of carbon black can be expressed by the degree of crystallinity, which is the ratio of the area of the G band measured in the Raman spectrum to the sum of the areas of the G band and the D band (S G / S G+D ). The crystallinity of the carbon black of the present invention is 39% or more, for example, 39% to 46%, which is significantly improved compared to conventional carbon black. As can be seen from this, the carbon black of the present invention has a high degree of graphitization. When the carbon black of the present invention is used as a conductive agent or support, the high graphitization of the carbon black can improve the conductivity of the electrode active material and compatibility with the electrolyte, and can increase the stability of the support material, thereby ensuring catalytic activity. The crystallinity of the carbon black of the present invention is 39%, 40%, 42%, 43%, 44%, 45%, or 46%, or a range consisting of any two values therein.

[0039] The Raman spectrum measurement method and parameters of the present invention are as follows:

[0040] Using a laser Raman spectrometer, multiple particles to be measured were placed on a glass slide and rubbed with a spatula multiple times to make it flat, and measurements were performed under the following conditions: YAG laser (excitation wavelength) 514 nm, groove count 600 gr / mm, filter D0.6, objective lens magnification 100x, exposure time 150 seconds, and cumulative number of measurements 2.

[0041] The BET specific surface area is measured according to the method of GB / T 19587-2004. Generally, the BET specific surface area of carbon black can reflect the development of the pore structure of the carbon black. The BET specific surface area of the present invention is 200 m 2 / g~763m 2 / g, which indicates that the carbon black has a well-developed void structure and branched structure. This increases the number of contact points between the carbon black and other materials, allowing the carbon black to fully exhibit its electrical conductivity and, at the same time, is advantageous for accommodating and supporting catalysts. In the carbon black of the present invention, the BET specific surface area of the carbon black is 200 m 2 / g, 213m 2 / g, 250m 2 / g, 300m 2 / g, 350m 2 / g, 400m 2 / g, 450m 2 / g, 500m 2 / g, 550m 2 / g, 572m 2 / g, 600m 2 / g, 650m 2 / g, 691m 2 / g, 700m 2 / g, 728m 2 / g, 763m 2 / g, or a range consisting of any two values therein.

[0042] At high temperatures and in an oxygen-deficient or oxygen-deprived environment, carbon black raw materials first decompose into small gas molecules and ions. These ions and molecules then accumulate and form cores (nucleation), forming primary carbon black particles. At high temperatures, the primary particles arrange into complex, chemically bonded, branched or chain-like aggregates, forming the primary carbon black structure. The primary structure is a permanent structure formed by strong chemical bonds between the aggregates. Electrostatic forces further aggregate the aggregates into larger agglomerates, forming the secondary carbon black structure. The secondary structure is a weak or unstable structure formed by van der Waals forces between the carbon black aggregates, and is not a permanent structure. The void volume resulting from these aggregated carbon black aggregates is a measure of carbon black structure and can be expressed as the oil absorption number (OAN). OAN was measured using the standard method "GB / T 3780.2-2017 Carbon Black Part 2: Determination of Oil Absorption." In the carbon black of the present invention, the OAN of the carbon black is 334 mL / 100 g, 360 mL / 100 g, 380 mL / 100 g, 400 mL / 100 g, 405 mL / 100 g, 420 mL / 100 g, 446 mL / 100 g, 450 mL / 100 g, 460 mL / 100 g, 480 mL / 100 g, 500 mL / 100 g, 548 mL / 100 g, or a range consisting of any two values therein.

[0043] The average particle size of the primary particles of the carbon black of the present invention is relatively small, 35 nm or less, for example, 25 nm to 35 nm. This increases the number of primary particles of the same mass of carbon black, further increasing the number of contact points, which is advantageous for forming many conductive paths. The average particle size of the primary particles of the carbon black of the present invention may be 25 nm, 28 nm, 30 nm, 32 nm, or 35 nm, or may be within a range consisting of any two values therein. The average particle size of the primary particles is the average value of particle sizes measured using photographs taken with a transmission electron microscope, and the particle size is the circle-equivalent diameter calculated from the area of the primary particles.

[0044] In a specific embodiment of the present invention, the crystallite size Lc of the carbon black is 20.03 Å to 25.17 Å.

[0045] The crystallite size Lc is one of the factors that represent the crystallinity of a carbon material having a crystalline structure, and can be calculated using the following Scherrer equation based on X-ray diffraction data obtained by XRD analysis. Scherrer's formula: Lc=0.89λ / (βCosθ) where 0.89 is the Scherrer constant, λ is the wavelength, θ is the angle at the peak corresponding to the spacing d(002), and β is the full width maximum at the peak corresponding to the spacing d(002).

[0046] The crystallite size Lc of the carbon black of the present invention is significantly increased compared to the crystallite size Lc of the raw carbon black, significantly improving the crystallinity of the carbon black and significantly improving the graphitization degree of the carbon black of the present invention. In the carbon black of the present invention, the crystallite size Lc is 20.03 Å, 20.5 Å, 21 Å, 21.5 Å, 22.14 Å, 23 Å, 23.5 Å, 24 Å, 24.5 Å, 25.17 Å, or a range consisting of any two values therein.

[0047] In a specific embodiment of the present invention, the crystallite size La of the carbon black is 27.8 Å to 37.5 Å.

[0048] The Raman spectrum of carbon is at approximately 1340 cm -1 and 1580cm -1 It contains two major "resonance" bands in the lattice, denoted as the "D" band and the "G" band, respectively. Usually, the D band is a disordered sp 2 Due to carbon, the G band is graphitic or "ordered" sp 2The following empirical relationship was obtained by regression analysis due to carbon: La = 43.5 × (G band area / D band area), where La is calculated in angstroms (Å). The crystalline domains of the ultra-high structure and high specific surface area carbon black of the present invention based on high crystallinity can be expressed by the crystallite size (La), which can be measured by Raman spectroscopy. La is defined as 43.5 × (G band area / D band area). The crystallite size indicates the degree of graphitization, with a higher La value indicating a higher degree of graphitization. The crystallite size La of the carbon black of the present invention is 27.8 Å to 37.5 Å, indicating that the carbon black of the present invention has a high degree of graphitization. In the carbon black of the present invention, the crystallite size La is 27.8 Å, 28 Å, 29 Å, 30 Å, 31.1 Å, 32 Å, 34 Å, 35 Å, 36 Å, 37.5 Å, or a range consisting of any two values therein.

[0049] In a specific embodiment of the present invention, the lattice fringes of the primary particles of carbon black exhibit an irregular hat-like or ring-like shape.

[0050] In a specific embodiment of the present invention, the carbon black aggregate size D 50 Furthermore, the aggregate size D of carbon black is 95 nm or less. 50 is 68nm or more.

[0051] The size distribution curve of the carbon black aggregates of the present invention was measured using a disc centrifuge particle size analyzer (Brookhaven Instruments Corporation, BI-DPP), and the measurement method was based on GB / T 3780.27-2020. The specific measurement method is as follows: (1) Preparation of carbon black dispersion: 20 mg of carbon black sample was weighed, 20 mL of dispersion (rotating solution:ethanol = 4:1 (volume ratio)) was added, the pH was adjusted to 9-10, and the dispersion was sonicated for 5 minutes at 50 W, followed by 10 minutes of sonication using a cell disruptor, and then another 5 minutes at 50 W. The carbon black dispersion was then allowed to cool to room temperature. Then, 0.5 g of Triton X-100 and 5 drops of ammonia water were mixed with soft water to prepare 1000 mL of rotating solution. (2) The host of the particle size analyzer was turned on and the device was allowed to stand for 30 minutes until it reached a stable state. (3) The computer of the particle size analyzer was started, and the relevant parameters were set as follows: measurement time: 60 min, rotation speed: 7000 r / min, particle density: 1.860 g / cm 3 and the temperature was 25°C. (4) Inject 1 mL of ethanol using the needle tube, press the motor at the same time, and immediately inject 15 mL of rotating liquid and 0.1 mL of dodecane in sequence. After waiting 3 to 5 minutes, when the signal value stabilizes, add 0.25 mL of carbon black dispersion, start the instrument measurement program, and after about 30 to 60 minutes, stop the measurement when the signal value approaches the baseline, click zoom to adjust the baseline so that the baseline region is parallel, and perform two repeated measurements for each measurement sample.

[0052] D 50 is the particle size corresponding to the cumulative particle size distribution percentage of carbon black agglomerate particles reaching 50%. The aggregate size distribution of the carbon black produced in the present invention is similar to the aggregate size distribution curve of the raw carbon black, and D 50 From the numerical values, it can be seen that the carbon black of the present invention after oxidative etching maintains the aggregate structural size of the raw carbon black, does not destroy the abundant branched structure of the carbon black, and has excellent liquid absorption and retention capabilities. 50is 68 nm to 95 nm, for example, 68 nm, 72 nm, 75 nm, 78 nm, 80 nm, 82 nm, 84 nm, 88 nm, 90 nm, 95 nm, or a range consisting of any two values therein.

[0053] In a specific embodiment of the present invention, the average lattice spacing d(002) of carbon black is 0.3534 nm or less, for example, 0.3479 nm to 0.3534 nm.

[0054] The degree of graphitization of a carbon material can be expressed by its "spacing d." The average lattice spacing d(002) of the present invention is defined as the average distance between adjacent hexagonal rings in the c-axis direction and is determined by the XRD (002) diffraction peak. The spacing d(002) can be calculated using the following formula based on Bragg's law: d=λ / (2Sinθ) where λ is the wavelength of the radiation source (for copper, λ is 1.54 Å), θ is the diffraction angle in degrees (peak 002), and d is the spacing between two carbon layer planes.

[0055] The conductive carbon black of the present invention has an average lattice spacing d(002) of 0.3534 nm or less, for example, 0.3479 nm to 0.3534 nm. The d(002) spacing of the raw carbon black is significantly reduced, which indicates that the etching process of the present invention reduces the lattice spacing and improves the crystallinity of the carbon black. Furthermore, the d(002) of the carbon black of the present invention is close to or less than 0.3500 nm, which indicates that the carbon black of the present invention is graphitic carbon and improves the stability of the carbon black. In various embodiments, the average lattice spacing d(002) of the carbon black of the present invention is 0.3479 nm, 0.349 nm, 0.35 nm, 0.351 nm, 0.3515 nm, 0.352 nm, 0.3525 nm, 0.353 nm, or 0.3534 nm, or a range consisting of any two values therein.

[0056] In a specific embodiment of the present invention, the average pore diameter of the carbon black is 5.86 nm to 9.04 nm. In various embodiments, the average pore diameter of the carbon black is 5.86 nm, 6 nm, 6.2 nm, 6.4 nm, 6.59 nm, 6.8 nm, 7 nm, 7.2 nm, 7.41 nm, 8.5 nm, 9.04 nm, or a range consisting of any two values therein.

[0057] In a specific embodiment of the present invention, the carbon black has a pore volume of 2 nm to 50 nm in size measured by nitrogen adsorption / desorption of 0.3157 cm 3 / g~1.2061cm 3 In a different embodiment, the volume of pores with a size between 2 nm and 50 nm is 0.3157 cm 3 / g, 0.4cm 3 / g, 0.5cm 3 / g, 0.6540cm 3 / g, 0.7cm 3 / g, 0.8cm 3 / g, 0.85cm 3 / g, 0.8689cm 3 / g, 1.2061cm 3 / g, or a range consisting of any two values therein.

[0058] In a specific embodiment of the present invention, the ratio of the volume of pores having a size of 2 nm to 50 nm to the total volume of pores in the carbon black is 84.6% or more, for example, 84.6% to 93.8%. In different embodiments, the ratio of the volume of pores having a size of 2 nm to 50 nm to the total volume of pores is 84.6%, 85%, 86.9%, 87%, 88%, 88.9%, 93.8%, or a range consisting of any two values therein.

[0059] The present invention measures the pore parameters according to the method of GB / T 19587-2004. The pore volume of the carbon black of the present invention is 0.9773 cm 3 / g, and the pore volume ratio of mesopores (2 nm to 50 nm) is 84.6% or more, which significantly improves the volume ratio of mesopores compared to the raw carbon black, enhancing the liquid retention capacity of the carbon black and favoring catalyst support. The developed mesopore structure and large BET specific surface area indicate that the carbon black of the present invention has a developed pore structure.

[0060] Another aspect of the present invention provides a method for producing any of the above carbon blacks, comprising the steps of:

[0061] The pretreated raw carbon black is subjected to an activation etching treatment.

[0062] The activation etching process involves heating the substrate to a first activation temperature in a protective atmosphere, performing an activation process under the action of an activation gas, cooling the substrate to a second activation temperature, performing an etching process under the action of an activation gas, and then lowering the temperature to room temperature in a protective atmosphere.

[0063] The pretreatment involves placing the raw carbon black in an aqueous solution containing an oxidizing agent, treating it at 30°C to 150°C for 0.5 to 2 hours, and then washing and drying it.

[0064] The first activation temperature is 1100°C to 1500°C, the second activation temperature is 900°C to 1000°C, and the crystallinity of the raw material carbon black is 44% or higher.

[0065] The present invention uses raw carbon black with a certain degree of graphitization, and the surface of the primary particles of the raw carbon black has a high degree of graphitization. The crystallinity of the raw carbon black of the present invention is 44% or more, for example, 44%, 45%, 46%, 48%, 50%, 51%, or a range consisting of any two values therein. The raw carbon black of the present invention comprises a "shell" of relatively large, perfect crystallites, which generally have layered planes oriented parallel to the particle surface, minimizing defects on the surface of the primary particles of the raw carbon black. The central region or "core" of the "shell" is primarily composed of small, imperfect crystallites, single layer planes, and irregular carbon not bonded within the layered planes, i.e., "defects." In the present invention, raw carbon black is first pretreated with an oxidizing agent to oxidize the carbon black. Then, at higher temperatures (1100-1500°C), activated gas molecules (e.g., water molecules) and oxygen-containing functional groups generated by the initial oxidation attack the "defects" on the carbon surface, removing carbon atoms from the surface to form gaseous CO or CO and hydrogen gas, exposing more carbon atoms or amorphous carbon and creating more "defects." This is known as activation. Then, at an appropriate temperature (900-1000°C), the carbon in the "core" is selectively etched to form carbon black with a high specific surface area and high structure. At the same time, the "shell" has a high degree of graphitization, preventing dissociation or collapse of some defects during the oxidative etching process. This ensures the grape-like porous branch structure and maintains the aggregate structure of the raw carbon black, resulting in good liquid absorption and retention and excellent electrical conductivity.

[0066] Appropriate pretreatment temperature and time can form appropriate defects on the carbon surface during the initial oxidation process and generate appropriate oxygen-containing functional groups. In various embodiments, the pretreatment involves placing the raw carbon black in an aqueous solution containing an oxidizing agent, and the treatment temperature is 30°C, 50°C, 80°C, 100°C, 120°C, 150°C, or any two values within the range. The treatment time is 0.5 hours, 0.8 hours, 1 hour, 1.5 hours, 2 hours, or any two values within the range.

[0067] At the higher temperature, i.e., the first activation temperature, in the present invention, the activation gas molecules and oxygen-containing functional groups generated by the initial oxidation attack defects on the carbon surface, forming a new gas phase and creating many defects. In the production method of the present invention, the first activation temperature is 1100°C, 1200°C, 1300°C, 1400°C, 1500°C, or a range consisting of any two values therein.

[0068] The second activation temperature of the present invention is relatively low, and under these temperature conditions, the "core" of the carbon black is selectively etched to form carbon black with a high specific surface area and high structure, while avoiding excessive etching and maintaining the existing structure to avoid excessive destruction. In the production method of the present invention, the second activation temperature is 900°C, 920°C, 940°C, 950°C, 960°C, 980°C, 1000°C, or a range consisting of any two values therein.

[0069] The protective atmosphere of the present invention can contain at least one of nitrogen gas and argon gas. By cooling under a protective atmosphere, it is possible to prevent a decrease in crystallinity due to oxidation of the product surface by oxygen and to remove functional groups on the product surface.

[0070] In a specific embodiment of the present invention, the BET specific surface area of the raw carbon black is 60 to 150 m 2 / g.

[0071] In the production method of the present invention, the BET specific surface area of the raw material carbon black is not limited. For example, 2 / g, 70m 2 / g, 80m 2 / g, 90m 2 / g, 100m 2 / g, 110m 2 / g, 120m 2 / g, 130m 2 / g, 140m 2 / g, 150m 2 The carbon black may be raw material carbon black such as, but not limited to, carbon black having a molecular weight of 1.001 or less.

[0072] In a specific embodiment of the present invention, the raw carbon black is acetylene carbon black.

[0073] In a specific embodiment of the present invention, the activation gas comprises at least one of nitrogen dioxide, nitric oxide, CO2, CO, oxygen gas, ozone, and water vapor.

[0074] The activation gas attacks defects on the carbon surface during the activation process, exposing many carbon atoms or amorphous carbon. In actual operation, the activation gases used in the activation treatment at the first activation temperature and the heat-retention treatment at the second activation temperature may be the same or different.

[0075] In a specific embodiment of the present invention, the activation treatment time at the first activation temperature is 10 minutes to 30 minutes.

[0076] By adjusting the activation time, the state of defects formed on the carbon surface of the raw carbon black at the first activation temperature can be adjusted, and an appropriate activation time helps to ensure structural stability while also preventing defect formation. The activation time of the present invention is 10 minutes, 15 minutes, 20 minutes, 25 minutes, 30 minutes, or a range consisting of any two values therein.

[0077] In a specific embodiment of the present invention, the duration of the etching treatment at the second activation temperature is 30 to 70 minutes.

[0078] By performing the etching at the second activation temperature for a certain period of time, etching can be focused on the "core" of the carbon black, increasing the mesopore structure, while at the same time avoiding the collapse or dissociation of the primary particles of the carbon black due to excessively long etching times. The etching time at the second activation temperature of the present invention is 30 minutes, 40 minutes, 50 minutes, 60 minutes, 70 minutes, or a range consisting of any two of these values.

[0079] In a specific embodiment of the present invention, the temperature is lowered at a rate of 2°C / min to 4°C / min, for example, 2°C / min, 2.5°C / min, 3°C / min, 3.5°C / min, 4°C / min, etc.

[0080] In a specific embodiment of the present invention, the temperature rise rate is 4°C / min to 6°C / min, for example, 4°C / min, 4.5°C / min, 5°C / min, 5.5°C / min, 6°C / min, etc.

[0081] In a specific embodiment of the present invention, the oxidizing agent comprises hydrogen peroxide and at least one of an oxoacid, including at least one of nitric acid, sulfuric acid, hypochlorous acid, and perchloric acid.

[0082] In actual operation, the mass fraction of the oxidizing agent in the oxidizing agent-containing aqueous solution is 20% to 70%, and may be, for example, but not limited to, 20%, 35%, 50%, 60%, 70%, etc. The amount of the oxidizing agent-containing aqueous solution used is not limited as long as it can immerse the raw material carbon black.

[0083] Yet another aspect of the present invention provides an electrode slurry containing any of the above carbon blacks.

[0084] Yet another aspect of the present invention provides a secondary battery comprising a positive electrode, a negative electrode, an electrolyte, and a separator, wherein at least one of the positive electrode and the negative electrode is produced from any of the electrode slurries described above.

[0085] Here, the types of the positive electrode active material, the negative electrode active material, the electrolyte, and the separator are not limited to any one type and can be adjusted according to actual needs. In the following examples, only one type of active material, electrolyte, and separator is used for illustrative purposes, and the types are not limited thereto.

[0086] Yet another aspect of the present invention provides a fuel cell comprising a catalyst, the catalyst comprising a support and active catalyst particles supported on the support, the support comprising carbon black.

[0087] The carbon black of the present invention is used as a catalyst support in fuel cells. Its ultra-high structure and high specific surface area maximize the contact between the reactants and the catalyst, thereby increasing catalytic efficiency. At the same time, the carbon black of the present invention has a stable structure, improving the durability of the catalyst support and extending the life of the battery. The type of active catalyst particles in fuel cells can be adjusted according to actual needs and is not limited to any one type. [Example]

[0088] The raw carbon black used in the following examples is acetylene carbon black, and its BET specific surface area is 143 m 2 / g and the crystallinity is 44%, but is not limited thereto.

[0089] Example 1 This example provides a method for preparing ultra-high structure and high specific surface area carbon black based on high crystallinity, which includes the following steps: (1) The raw carbon black was added to a 20 wt% aqueous hydrogen peroxide solution and treated at 30°C for 0.5 hours. After that, it was washed with water and dried to obtain pretreated raw carbon black. (2) The raw carbon black sample pretreated in step (1) was placed in a rotary furnace and protected by nitrogen gas. The furnace temperature was then increased to 1100°C at a rate of 5°C / min. The nitrogen gas was then turned off, nitrogen dioxide was introduced, and the temperature was maintained for another 10 minutes. The nitrogen dioxide gas was then turned off, water vapor was introduced, and the furnace temperature was decreased to 900°C at a rate of 3°C / min. The temperature was maintained for another 30 minutes. (3) The water vapor was turned off, nitrogen gas was introduced, and the mixture was allowed to cool naturally to room temperature under nitrogen gas protection, yielding carbon black with an ultra-high structure and a high specific surface area due to its high crystallinity.

[0090] Example 2 This example provides a method for preparing ultra-high structure and high specific surface area carbon black based on high crystallinity, which includes the following steps: (1) The raw carbon black was added to a nitric acid aqueous solution with a mass fraction of 35 wt%, treated at 60°C for 1 hour, washed with water, and dried to obtain pretreated raw carbon black. (2) The raw carbon black sample pretreated in step (1) was placed in a rotary furnace and protected by nitrogen gas. The furnace temperature was then increased to 1100°C at a rate of 5°C / min, after which the nitrogen gas was turned off and water vapor was introduced and the temperature was maintained for an additional 20 minutes. The furnace temperature was then decreased to 900°C at a rate of 3°C / min and maintained for an additional 50 minutes. (3) The water vapor was turned off, nitrogen gas was introduced, and the mixture was allowed to cool naturally to room temperature under nitrogen gas protection, yielding carbon black with an ultra-high structure and a high specific surface area due to its high crystallinity.

[0091] Example 3 This example provides a method for preparing ultra-high structure and high specific surface area carbon black based on high crystallinity, which includes the following steps: (1) The raw carbon black was added to a nitric acid aqueous solution with a mass fraction of 75 wt%, treated at 150°C for 2 hours, washed with water, and dried to obtain pretreated raw carbon black. (2) The raw carbon black sample pretreated in step (1) was placed in a rotary furnace and protected by nitrogen gas. The furnace temperature was then increased to 1400°C at a rate of 5°C / min, the nitrogen gas was then turned off, water vapor was introduced, and the temperature was maintained for an additional 30 minutes. The furnace temperature was then decreased to 1000°C at a rate of 3°C / min, and the temperature was maintained for an additional 70 minutes. (3) The water vapor was turned off, nitrogen gas was introduced, and the mixture was allowed to cool naturally to room temperature under nitrogen gas protection, yielding carbon black with an ultra-high structure and a high specific surface area due to its high crystallinity.

[0092] Example 4 This embodiment provides a method for manufacturing a battery, which includes the following steps: (1) Positive electrode active materials, lithium iron phosphate, polyvinylidene fluoride, and carbon black, were weighed in a mass ratio of 96:2:2 and uniformly mixed in an appropriate amount of N-methyl-2-pyrrolidone to obtain an electrode slurry. (2) The electrode slurry obtained in step (1) was applied onto an aluminum foil (current collector) having a thickness of 16 μm, and then dried, roll-pressed, and cut to prepare a positive electrode sheet. (3) A button battery was fabricated using a metallic lithium sheet as the counter electrode, a separator (model number: Celgard 2500), and an electrolyte (1 mol / L lithium hexafluorophosphate dissolved in a 1:1:1 volume ratio of dimethyl carbonate (DMC) / ethylene carbonate (EC) / ethyl methyl carbonate (EMC)).

[0093] Here, the carbon black used in the electrode slurry of each battery was the carbon black obtained in Examples 1 to 3, and the numbers corresponding to the obtained batteries are Example 4-1, Example 4-2, and Example 4-3, respectively.

[0094] Comparative Example 1 Comparative Example 1 provides a method for producing a carbon black product, including the following steps: (1) The raw carbon black was added to a 35 wt% aqueous nitric acid solution and treated at 150°C for 2 hours. After that, it was washed with water and dried to obtain pretreated raw carbon black. (2) The raw carbon black sample pretreated in step (1) was placed in a rotary furnace and protected by nitrogen gas. The furnace temperature was then increased to 1500°C at a rate of 5°C / min, the nitrogen gas was then turned off, water vapor was introduced, and the temperature was maintained for another 30 minutes. The furnace temperature was then decreased to 1050°C at a rate of 3°C / min, and the temperature was maintained for another 70 minutes. (3) The water vapor was turned off, nitrogen gas was introduced, and the mixture was allowed to cool to room temperature under nitrogen gas protection to obtain a carbon black product.

[0095] Comparative Example 1 further provides a battery with the manufacturing method of Example 4. The only difference is that the carbon black is replaced with the carbon black of Comparative Example 1 by the same weight, and the resulting battery number is Comparative Example 1-1.

[0096] Comparative Example 2 Comparative Example 2 provided a commercially available carbon black.

[0097] Comparative Example 2 further provides a battery, which refers to the manufacturing method of Example 4. The only difference is that the carbon black is replaced with the carbon black of Comparative Example 2 by the same weight, and the resulting battery number is Comparative Example 2-1.

[0098] Experimental Example 1 FIG. 1 shows scanning electron micrographs of the carbon black obtained in Example 3 of the present invention, and FIG. 2 shows transmission electron micrographs of the carbon black obtained in Example 3 of the present invention at different magnifications. As can be seen from the figures, the high-crystallinity, ultra-high-structure, high-specific-surface-area carbon black produced in this example of the present invention has a microstructure similar to that of the raw carbon black, with a grape-like porous branch structure. This indicates that the oxidative etching of the present invention does not destroy the structure of the carbon black aggregates and provides excellent liquid absorption and retention. Furthermore, the oxidative etching of the carbon black increases the mesopore structure, and some of the carbon black primary particles are hollowed out by etching, thereby improving the carbon black's liquid absorption and retention capacity and increasing the number of ionic conduction paths. Furthermore, as can be seen from the transmission electron micrographs, the carbon black produced in this example has band-like or ring-like lattice fringes, and the carbon black produced in this example has a higher degree of graphitization.

[0099] Furthermore, as can be seen from a transmission electron microscope, the primary particles of the carbon black produced according to the present invention are approximately spherical, and the primary particles of the carbon black do not collapse or dissociate due to oxidative etching. The average particle size of the primary particles of the carbon black of the present invention is 25 nm to 35 nm. Specifically, the average particle sizes of the primary particles of the carbon blacks of Examples 1 to 3 are shown in Table 1.

[0100] [Table 1]

[0101] Experimental Example 2 Raman spectroscopy was performed on the carbon blacks produced in different examples and comparative examples. The specific measurement method is as follows: Using a laser Raman spectrometer, multiple carbon black samples to be measured were placed on a glass slide and rubbed multiple times with a spatula to make it flat. Measurements were performed under the following measurement conditions: YAG laser (excitation wavelength) 514 nm, groove count 600 gr / mm, filter D0.6, objective lens magnification 100x, exposure time 150 seconds, and cumulative number of measurements 2.

[0102] Figures 3 to 5 show Raman spectra of the carbon blacks obtained in Examples 1 to 3 of the present invention, respectively. Figure 6 shows the Raman spectrum of the raw carbon black used in the examples of the present invention. Figures 7 and 8 show the Raman spectra of the carbon blacks in Comparative Examples 1 and 2, respectively. As can be seen from the figures, the Raman spectra of the carbon blacks produced in the present invention each have two characteristic peaks: a D Raman scattering peak and a G Raman scattering peak. The crystallite size La and crystallinity of the carbon blacks calculated based on the Raman spectra are shown in Table 2.

[0103] [Table 2]

[0104] The crystallite size La indicates the degree of graphitization, with a higher La value indicating a higher degree of graphitization. As can be seen from the above results, the carbon black produced according to the present invention has a high degree of graphitization. The crystallite size La of the carbon black of Comparative Example 1 was 26.8 Å, much lower than that of the raw carbon black. This is because the crystallites of the raw carbon black of Comparative Example 1 were severely etched and dissociated. As can be seen from this, excessive etching can increase the specific surface area of carbon black, but it also rapidly reduces the crystallinity, affecting the performance of the carbon black. The carbon black produced according to the present invention has a high degree of graphitization and is superior to the commercially available carbon black of Comparative Example 2. When the carbon black produced according to the present invention is used as a conductive agent or support, the high graphitization of the carbon black can improve the conductivity of the electrode active material and its compatibility with the electrolyte, and can also enhance the stability of the support material, thereby ensuring catalytic activity.

[0105] Furthermore, the BET specific surface area and pore size distribution of the carbon black samples from different examples and comparative examples were measured according to the method of GB / T 19587-2004. Specifically, the specific surface area and pore size distribution of the carbon black samples were measured using nitrogen gas adsorption. The samples were vacuum degassed at 250°C for 2 hours, and then the N adsorption / desorption performance of the samples was measured at liquid nitrogen (77K) temperatures in the range of p / p 00 to 1. The specific surface area of the carbon black was determined using the BET multipoint method, the micropore area and micropore volume of the samples were analyzed using the t-plot method, and the pore size distribution of the carbon black was calculated using the DFT method (a QSDFT model of N adsorption into slit-shaped carbon pores at 77K). The specific results are shown in Table 3.

[0106] [Table 3]

[0107] As can be seen from the above data, the pore volume of the carbon black produced by the present invention is 1.2859 cm 3 / g, and the pore volume ratio of mesopores (2 nm to 50 nm) was 84.6% or more in all cases. Compared with the raw material carbon black and the carbon black of Comparative Example 2, the pore volume ratio of mesopores was improved in both cases, enhancing the liquid retention capacity of the carbon black and being advantageous for catalyst support.

[0108] The OAN of the carbon blacks in different examples and comparative examples was measured according to the standard method of "GB / T 3780.2-2017 Carbon Black Part 2: Determination of Oil Absorption", and the specific results are shown in Table 4.

[0109] [Table 4]

[0110] The OAN of the carbon blacks obtained in Examples 1 to 3 of the present invention increased compared to the OAN of the raw carbon black, reaching a maximum increase of 50.9%, which gives the structure sufficient length and liquid absorption and retention capacity when used as a conductive agent, thereby achieving good electrical conductivity and ion conductivity. Furthermore, the carbon black obtained in Comparative Example 1 was excessively etched, resulting in an unstable aggregate structure that was prone to breakage, and some aggregates were destroyed by etching to form smaller aggregates, so its oil absorption did not increase significantly as etching progressed.

[0111] Experimental Example 3 The size distribution curves of the carbon black agglomerates were measured using a disc centrifuge particle size analyzer (Brookhaven Instruments Corporation, BI-DPP). The size distribution curves of the carbon black agglomerates obtained in Examples 1 to 3 are shown in Figures 9 to 11, the size distribution curve of the raw carbon black used in the Examples is shown in Figure 12, and the size distribution curves of the carbon black agglomerates in Comparative Examples 1 and 2 are shown in Figures 13 and 14. Based on the above results, the carbon black agglomerate size D50 was calculated. The results are shown in Table 5.

[0112] [Table 5]

[0113] As can be seen from the above measurement results, the size distribution curves of the carbon black aggregates produced in Examples 1 to 3 are almost unchanged from the size distribution curve of the raw carbon black aggregates, and are similar to the size distribution curve of the commercially available carbon black aggregates in Comparative Example 2. 50 From the numerical values, it can be seen that the carbon black after oxidative etching of the present invention retains the aggregate structure size of the raw carbon black and does not substantially destroy the abundant branched structure of the carbon black, which is consistent with the results of scanning electron microscopy and transmission electron microscopy. The carbon black produced in Comparative Example 1 was excessively etched, resulting in an unstable aggregate structure that was prone to breakage, or the aggregates were destroyed by etching and became smaller aggregates. This resulted in a significant decrease in aggregate particle size compared to the raw carbon black and the carbon blacks produced in Examples 1 to 3, which affected the liquid absorption and retention capacity of the carbon black.

[0114] Figure 15 shows the XRD patterns of the carbon blacks and raw carbon blacks of Examples 1-3 and Comparative Examples 1-2 of the present invention. Calculations based on the XRD pattern data reveal that the average lattice spacing d(002) of the carbon blacks of Examples 1-3 is 0.3534 nm, 0.3510 nm, and 0.3479 nm, respectively. However, the average lattice spacing d(002) of the raw carbon black is 0.3546 nm. The average lattice spacing d(002) of the carbon black obtained by etching is smaller than the average lattice spacing d(002) of the raw carbon black. Surface etching reduces the lattice spacing and improves the crystallinity of the carbon black. Furthermore, the average lattice spacing d(002) of the carbon blacks obtained in Examples 1-3 is close to or less than 3.500 nm. This indicates that the carbon blacks obtained in Examples 1-3 are graphitic carbons, enhancing the stability of the carbon black. The average lattice plane spacing d(002) of the commercially available carbon black in Comparative Example 2 was 0.3591 nm, and the average lattice plane spacing d(002) of Examples 1 to 3 of the present invention was significantly reduced compared to Comparative Example 2. As can be seen from this, the graphitization degrees of the carbon blacks obtained in Examples 1 to 3 were higher than that of the commercially available carbon black. The average lattice plane spacing d(002) of the carbon black produced in Comparative Example 1 was 0.3725 nm, which was much higher than the d(002) of graphitic carbon. As can be seen from this, excessive etching reduced the graphitization degree of the carbon black.

[0115] 15, the crystallite sizes Lc of the carbon blacks produced in Examples 1 to 3 of the present invention were 25.17 Å, 22.14 Å, and 20.03 Å, respectively. The crystallite size Lc of the raw carbon black was 18.17 Å, and the crystallite size Lc of the commercially available carbon black of Comparative Example 2 was 17.16 Å. As can be seen, the crystallite size Lc of the carbon black produced in the examples of the present invention was 38.5% larger than that of the raw carbon black, significantly improving the crystallinity of the carbon black, which is consistent with the analysis of the average lattice plane spacing d(002). Furthermore, the crystallite size Lc of the carbon black produced in the examples of the present invention was also significantly larger than that of the commercially available carbon black. As can be seen, the graphitization degree of the carbon black produced in the examples of the present invention was higher than that of the commercially available carbon black. In addition, the crystallite size Lc of the carbon black produced in Comparative Example 1 was 11.02 Å, which was much lower than the crystallite size Lc of the carbon blacks in Examples 1 to 3 and Comparative Example 2. This suggests that the crystallites were dissociated by severe etching, which significantly reduced the crystallite size Lc of the carbon black produced in Comparative Example 1 and reduced the crystallinity.

[0116] Experimental Example 4

[0117] The performance of the batteries obtained in Example 4 and Comparative Examples 1 and 2 was measured, and the measurement method included the following steps. (1) Discharge measurement method at low temperature of -20℃: The assembled button battery is left at room temperature for 16 hours, and then charged and discharged three times at a small current of 0.1C. The battery is then placed in a thermostatic chamber at 25℃ and charged and discharged at 1C. It is then fully charged, and the fully charged battery is placed in a thermostatic chamber at -20℃ and left for 12 hours. Finally, it is discharged at 1C. The ratio of the discharge capacity at -20℃ to the discharge capacity at 25℃ is the low-temperature discharge efficiency at -20℃. (2) High-temperature discharge measurement method at 55°C: The assembled button battery is left at room temperature for 16 hours, and then charged and discharged three times at a small current of 0.1C. The battery is then placed in a thermostatic chamber at 25°C and charged and discharged at 1C. It is then fully charged, and the fully charged battery is placed in a thermostatic chamber at 55°C and left for 5 hours. Finally, it is discharged at 1C. The ratio of the discharge capacity at 55°C to the discharge capacity at 25°C is the high-temperature discharge efficiency at 55°C.

[0118] The specific measurement results are shown in Table 6. [Table 6]

[0119] At low temperatures, lithium ions have low energy and poor transport capacity, but ions must overcome particle interface barriers to transport. For the same amount of carbon black added, a high specific surface area results in a large number of particles distributed on and covering the surfaces of active particles, forming a good conductive network, reducing ion transport paths and improving the conductive ability of the active material at low temperatures. Furthermore, a high degree of crystallinity in carbon black reduces surface resistivity, improves electron transport speed, and is advantageous for increasing low-temperature discharge capacity and discharge efficiency. On the other hand, Comparative Example 2 had a high specific surface area, but low crystallinity and many defects. Therefore, the amount of conductive carbon black was lower than that of Example 3 of the present invention. Therefore, the batteries of Examples 4 and 3 had slightly better low-temperature discharge efficiency than the batteries of Comparative Examples 2 and 1.

[0120] Although high-temperature discharge is advantageous for increasing discharge capacity, carbon black with a high specific surface area is prone to side reactions at high temperatures, and carbon black with a low degree of crystallinity in particular has many defects, exacerbating the occurrence of side reactions. The carbon blacks of Example 3 and Comparative Example 2 have high specific surface areas and low degrees of crystallinity, and the high-temperature discharge efficiencies of the corresponding batteries are lower than those of the batteries containing the carbon blacks of Examples 1 and 2. On the other hand, the carbon black of Example 3 has a higher degree of crystallinity than the carbon black of Comparative Example 2, and therefore the high-temperature discharge efficiencies of the batteries of Examples 4 and 3 were slightly better than those of the batteries of Comparative Examples 2 and 1.

[0121] Furthermore, as can be seen from the above low-temperature and high-temperature performance measurement results, although the carbon black produced in Comparative Example 1 had a high comparative value, it had a low degree of crystallinity, a low intrinsic conductivity, and was prone to side reactions. As a result, the discharge efficiencies of the produced button batteries at -20°C and 55°C were both lower than the discharge efficiencies of the batteries corresponding to the carbon blacks of the other Examples.

[0122] Finally, it should be noted that the above embodiments are merely for illustrating the technical solutions of the present invention, and are not intended to limit the same. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art may modify the technical solutions described in the above embodiments, and may equally replace some or all of the technical features therein. These modifications or replacements do not deviate from the essence of the corresponding technical solutions and the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A carbon black having an ultra-high structure and a high specific surface area based on high crystallinity, said carbon black satisfying the following conditions: (1) The crystallinity is 39% or more, (2) BET specific surface area is 200 to 763 m ２ / g, (3) OAN is 334 to 548 mL / 100 g; (4) The average particle size of the primary particles is 35 nm or less. Carbon black characterized by an ultra-high structure and a high specific surface area due to its high crystallinity.

2. At least one of the following conditions is met: (1) The carbon black has a crystallite size Lc of 20.03 Å to 25.17 Å; (2) The carbon black has an average lattice spacing d(002) of 0.3534 nm or less; Preferably, the carbon black has an average lattice spacing d(002) of 0.3479 nm to 0.3534 nm.