Conductive carbon black, method for producing the same, and lithium battery

Abstract

The application provides a conductive carbon black, a preparation method thereof and a lithium battery. The preparation method comprises the following steps: mixing raw carbon black and a halogenation reagent, and performing halogenation treatment in a protective atmosphere to obtain a conductive carbon black precursor; mixing carbon black acetylation reagent and cuprous salt, and performing activation treatment in a protective atmosphere to obtain activated acetylation reagent; mixing the activated acetylation reagent and the conductive carbon black precursor, and performing carbon black acetylation treatment in a protective atmosphere to obtain a conductive carbon black semi-finished product; and performing deprotection treatment on the conductive carbon black semi-finished product to obtain the conductive carbon black. The application further provides the conductive carbon black obtained by the above preparation method, and a lithium battery made of the conductive carbon black. The conductive carbon black of the application greatly prolongs the cycle life of the lithium battery without affecting other battery performances.

Description

Technical Field

[0001] This invention relates to the field of lithium-ion battery manufacturing technology, and in particular to a conductive carbon black, its preparation method, and a lithium battery. Background Technology

[0002] Lithium-ion batteries are high-energy-density energy storage devices, widely used in all aspects of daily life and work due to their excellent overall performance. Internally, a lithium-ion battery consists of a positive electrode and a negative electrode separated by a flexible separator or a rigid solid electrolyte. The positive electrode is formed by uniformly coating a slurry consisting of positive electrode active material, conductive additives, and binders onto the surface of aluminum foil and then drying it. The negative electrode is formed by uniformly coating a slurry consisting of negative electrode active material, conductive additives, binders, and thickeners onto the surface of copper foil and then drying it. Lithium ions cycle between the positive and negative electrodes using an electrolyte or a solid / semi-solid electrolyte to achieve the charge-discharge cycle of the battery.

[0003] Currently, commercially available lithium-ion battery positive electrode active materials include nickel-cobalt-manganese ternary cathode materials, nickel-cobalt-aluminum ternary cathode materials, lithium iron phosphate cathode materials, lithium manganese iron phosphate cathode materials, and lithium manganese oxide cathode materials. Commercially available negative electrode active materials include natural graphite, artificial graphite, silicon-based negative electrode materials, and lithium titanate negative electrode materials. Although these positive and negative electrode active materials each have their own performance advantages, they all share a common drawback: during the charging and discharging process of lithium-ion batteries, the positive and negative electrode active materials inevitably undergo volume expansion or contraction due to the insertion or extraction of lithium ions. This leads to frequent changes in the overall battery structure and internal stress. As the number of charge-discharge cycles of a lithium-ion battery increases, the structure of the positive and negative electrodes gradually deteriorates. When this deterioration reaches a certain level, it manifests as a significant decline in the overall performance of the battery, i.e., battery failure.

[0004] Currently, there are three main solutions proposed to address the above problems: 1) Developing active materials with minimal volume changes before and after lithium-ion insertion / extraction; 2) Developing higher-strength binders or increasing the amount of binder used in battery production; 3) Suppressing volume changes of the positive and negative electrodes by further increasing the rigidity of the cell's outer casing. However, the problem with solution 1 is that, theoretically, lithium-ion insertion / extraction inevitably causes changes in the lattice of the active material, leading to volume expansion / contraction, and this expansion / contraction becomes increasingly pronounced with the increase in the energy density of the active material. Therefore, developing active materials with smaller volume changes while pursuing higher energy density lithium batteries is quite challenging. The problem with solution 2 is that the types of polymer binders that can meet the high voltage and highly corrosive environment inside lithium batteries are relatively limited, while actual battery production and application conditions require the electrodes to have a certain degree of flexibility. Furthermore, currently commercially available lithium battery binders are all insulating materials, and increasing their usage will inevitably lead to a decrease in overall battery performance. The problem with solution 3 is that to improve the rigidity of the cell casing, either the thickness of the currently used stainless steel or aluminum alloy casing should be increased or reinforced structural components added, or a material with higher rigidity should be used. However, the above solutions all lead to a decrease in the overall energy density of the battery cell and an increase in cost, making them uneconomical. Therefore, to address the current problem of unsatisfactory cycle life of lithium batteries, a method is needed to improve the cycle stability of lithium batteries. Summary of the Invention

[0005] To address the aforementioned problems, the present invention aims to provide a conductive carbon black, its preparation method, and a lithium battery. The conductive carbon black obtained by this preparation method significantly extends the cycle life of lithium batteries without affecting other battery performance parameters.

[0006] To achieve the above objectives, the present invention provides a method for preparing conductive carbon black, the method comprising:

[0007] S1. Mix raw carbon black and halogenating reagent, and perform halogenation treatment in a protective atmosphere to obtain conductive carbon black precursor.

[0008] S2. Mix carbon black acetylation reagent and cuprous salt, and activate them in a protective atmosphere to obtain activated acetylation reagent.

[0009] S3. The activated acetylation reagent and the conductive carbon black precursor are mixed and subjected to carbon black acetylation treatment in a protective atmosphere to obtain conductive carbon black sub-product; the conductive carbon black sub-product is subjected to deprotection treatment to obtain conductive carbon black.

[0010] The above preparation method first grafts halogen-containing groups onto the surface of raw carbon black through a halogenation reaction, and then reacts the halogen-containing groups on the surface of the raw carbon black with an activated acetylation reagent, ultimately achieving the effect of modifying the carbon black surface with acetylation groups. This yields conductive carbon black with surface acetylation functionalization. During the lithium-ion battery formation stage, this conductive carbon black can undergo acetylation coupling reactions, forming strong conjugated and covalent bonds between carbon black particles. This improves the electron transport performance within the battery electrode, enhances the stability of the electrode structure, extends the battery cycle life, and does not affect other battery performance parameters.

[0011] The preparation method provided by this invention prepares high-performance conductive carbon black using furnace black and acetylene black. That is, the raw material carbon black may include carbon black produced by furnace black processing and / or carbon black produced by acetylene black processing.

[0012] In the above preparation method, the specific surface area of ​​the raw carbon black can be 120-560 μm. 2 / g, for example, but not limited to 122m 2 / g、145m 2 / g、183m 2 / g、211m 2 / g、242m 2 / g、254m 2 / g、278m 2 / g、315m 2 / g、343m 2 / g、375m 2 / g、433m 2 / g、455m 2 / g、510m 2 / g、558m 2 The specific values ​​such as / g and the range with any two of the above specific values ​​as endpoints.

[0013] In the above preparation method, the oil absorption value of the raw carbon black can be 130-330cc / 100g, such as, but not limited to, specific values ​​such as 130cc / 100g, 153cc / 100g, 171cc / 100g, 196cc / 100g, 202cc / 100g, 218cc / 100g, 230cc / 100g, 242cc / 100g, 247cc / 100g, 256cc / 100g, 275cc / 100g, 292cc / 100g, 310cc / 100g, 330cc / 100g, etc., and a range with any two of the above specific values ​​as endpoints.

[0014] In the above preparation method, the graphitization degree of the raw carbon black can be 20%-42%, for example, but not limited to specific values ​​such as 20.5%, 23.4%, 24.6%, 25.9%, 26.2%, 26.5%, 26.9%, 28.8%, 30.2%, 31.1%, 32.4%, 33.7%, 35.3%, 41.9%, etc., and the range with any two of the above specific values ​​as endpoints.

[0015] In the above preparation method, the iron content of the raw carbon black can be 0ppm-10ppm, for example, but not limited to specific values ​​such as 1ppm, 2ppm, 4ppm, 7ppm, 9ppm, etc., and the range with any two of the above specific values ​​as endpoints; the total content of the six elements nickel, cobalt, manganese, zinc, copper and chromium in the raw carbon black can be 0ppm-5ppm, for example, but not limited to specific values ​​such as 1ppm, 2ppm, 3ppm, 4ppm, etc., and the range with any two of the above specific values ​​as endpoints; the sulfur content in the raw carbon black can be 0ppm-800ppm, for example, but not limited to specific values ​​such as 94ppm, 106ppm, 175ppm, 193ppm, 227ppm, 295ppm, 319ppm, 325ppm, 364ppm, 429ppm, 523ppm, 568ppm, 704ppm, 733ppm, etc., and the range with any two of the above specific values ​​as endpoints.

[0016] In the above preparation method, the raw material carbon black can be in powder form. This invention does not impose any restrictions on other carbon black parameters not mentioned.

[0017] In the above preparation method, the halogenating reagent may include a mixture of iodine chloride, mercuric iodide and mercuric oxide (e.g., a mixture with a molar ratio of 1:1), N-iodosuccinimide, elemental bromine, and N-bromosuccinimide, or a solution of one or more of these.

[0018] In the above preparation method, in S1, the raw material carbon black and the halogenating reagent can be mixed in a first solvent to form a halogenated raw material solution, and then subjected to halogenation treatment. The first solvent is generally an aprotic solvent, and specifically may include one or a combination of two or more of the following: dichloromethane, n-hexane, cyclohexane, toluene, tetrahydrofuran, pyridine, formamide, N,N-dimethylformamide, dimethyl sulfoxide, diethyl ether, acetone, butanone, dioxane, and acetonitrile.

[0019] In the above preparation method, the halogenation treatment is carried out in a protective atmosphere, which may include a nitrogen atmosphere and / or an argon atmosphere.

[0020] In some specific implementations, the raw carbon black can be heated and dried before halogenation treatment. The drying temperature is 70-160°C, for example, but not limited to 70°C, 85°C, 100°C, 115°C, 130°C, 145°C, 160°C, and any two of the above specific values ​​as endpoints; the drying time is 6-24 hours, for example, but not limited to 6 hours, 12 hours, 18 hours, 24 hours, and any two of the above specific values ​​as endpoints.

[0021] In some specific implementations, the first solvent may also be dried before halogenation treatment so that the water content in the first solvent is not higher than 50 ppm.

[0022] In the above preparation method, the temperature of the halogenation treatment can be controlled to be 25-125℃, for example, but not limited to specific values ​​such as 25℃, 45℃, 60℃, 70℃, 90℃, 100℃, 112℃, 125℃, etc., and the range with any two of the above specific values ​​as endpoints; the time of the halogenation treatment can be controlled to be 12h-48h, for example, but not limited to specific values ​​such as 12h, 18h, 24h, 48h, etc., and the range with any two of the above specific values ​​as endpoints.

[0023] In the above preparation method, during step S1, stirring can be carried out during the mixing of the raw material carbon black and the halogenating reagent, and stirring can also be carried out during the halogenation process. The stirring speed can be 60-720 rpm, for example, but not limited to specific values ​​such as 60 rpm, 120 rpm, 240 rpm, 360 rpm, 720 rpm, etc., and a range with any two of the above specific values ​​as endpoints.

[0024] In the above preparation method, the ratio of the number of kilograms of raw carbon black to the number of moles of halogen atoms in the halogenating reagent can be controlled to be 1:(0.1-0.67) (that is, the ratio of the mass of raw carbon black to the molar amount of halogen atoms in the halogenating reagent is 1 kg:(0.1-0.67) mol), for example, but not limited to specific values ​​such as 1:0.1, 1:0.2, 1:0.3, 1:0.4, 1:0.55, 1:0.67, etc., and the range with any two of the above specific values ​​as endpoints.

[0025] In the above preparation method, the mass of the raw carbon black for halogenation treatment is 10%-25% of the total mass of the raw carbon black, halogenation reagent, and solvent (i.e., the total mass of the halogenation raw material solution), for example, but not limited to specific values ​​such as 10%, 15%, 18%, 20%, 23%, 25%, etc., and a range with any two of the above specific values ​​as endpoints.

[0026] In the above preparation method, the order of adding each reagent in the halogenation treatment of S1 can be: first add the first solvent, then add the raw material carbon black, and then add the halogenation reagent.

[0027] In the above preparation method, the halogenated product can undergo post-processing, such as sequential filtration, washing, and vacuum drying, before being used for carbon black acetylation treatment. The filtration is carried out in a protective atmosphere, which may include a nitrogen atmosphere and / or an argon atmosphere. The filtration can use any suction filtration device, and the filter medium may include a G4 sintered sand funnel and / or a G5 sintered sand funnel covered with medium-speed filter paper. The washing can use a dry aprotic solvent to rinse the filter residue, preferably the same solvent as the first solvent used in the halogenation treatment. The rinsing amount is preferably 2-3 times the amount of the first solvent used in the halogenation treatment, for example, but not limited to specific values ​​such as 2 times, 2.5 times, 3 times, etc., and a range with any two of the above specific values ​​as endpoints. The vacuum drying is the removal of residual solvent inside the filter residue under vacuum conditions. The vacuum drying temperature is 50-130℃, for example, but not limited to specific values ​​such as 50℃, 70℃, 80℃, 110℃, 130℃, etc., and any two of the above specific values ​​as endpoints. The vacuum drying time is 12-24h, for example, but not limited to specific values ​​such as 12h, 18h, 24h, etc., and any two of the above specific values ​​as endpoints.

[0028] In the above preparation method, the reaction efficiency of the halogenation reaction can be adjusted by controlling the type of halogenating reagent and the ratio between the raw material carbon black and the halogenating reagent in S1.

[0029] In the above preparation method, the carbon black acetylation reagent is generally an acetylation compound with a protecting group at the end, specifically including one or more of the following: trimethylsilylacetylene, lithium trimethylsilylacetylene, triethylsilylacetylene, tert-butyldimethylsilylacetylene, triisopropylsilylacetylene, dimethylphenylsilylacetylene, and triphenylsilylacetylene.

[0030] In the above preparation method, the cuprous salt can be used as an alkynyl activator to activate the alkynylating reagent. Compared with the alkynylating reagent that has not been activated by the cuprous salt, the alkynylating reagent activated by the cuprous salt can undergo a coupling reaction with the halogenated reagent, and the reaction efficiency is significantly improved. The cuprous salt is generally an inorganic or organic compound containing monovalent copper ions, and may specifically include one or a combination of two or more of cuprous iodide, cuprous bromide, cuprous chloride, cuprous sulfide, cuprous oxide, cuprous thiocyanate, cuprous acetate, cuprous selenide, and cuprous cyanide.

[0031] In the above preparation method, during the activation treatment, the molar ratio of the carbon black acetylation reagent to the cuprous salt can be controlled to be 1:(1.05-1.4), for example, but not limited to specific values ​​such as 1:1.05, 1:1.1, 1:1.2, 1:1.25, 1:1.3, 1:1.33, 1:1.4, and any two of the above specific values ​​as endpoints.

[0032] In the above preparation method, the carbon black acetylation reagent and the cuprous salt can be mixed in a second solvent to form an activated raw material solution, and then activated. The second solvent can be an aprotic solvent, specifically including one or more of the following: dichloromethane, N-methylpyrrolidone, butyl carbonate, pyridine, N,N-dimethylformamide, dimethyl sulfoxide, diethyl ether, isopropyl ether, petroleum ether, butanone, dioxane, dioxane, acetonitrile, and malononitrile.

[0033] In the above preparation method, the total concentration of the carbon black acetylation reagent and cuprous salt in the activated raw material solution can be 0.15-2 mol / L, for example, but not limited to specific values ​​such as 0.15 mol / L, 0.3 mol / L, 0.45 mol / L, 0.6 mol / L, 0.8 mol / L, 1 mol / L, 1.2 mol / L, 1.4 mol / L, 1.6 mol / L, 1.8 mol / L, 1.9 mol / L, 2 mol / L, etc., and a range with any two of the above specific values ​​as endpoints.

[0034] In the above preparation method, the activation temperature can be 25-100℃, for example, but not limited to specific values ​​such as 25℃, 35℃, 45℃, 65℃, 80℃, 100℃, etc., and the range with any two of the above specific values ​​as endpoints; the activation time can be 24h-48h, for example, but not limited to specific values ​​such as 24h, 36h, 48h, etc., and the range with any two of the above specific values ​​as endpoints.

[0035] In the above preparation method, the activation treatment is generally carried out in a protective atmosphere, which includes a nitrogen atmosphere and / or an argon atmosphere.

[0036] In the above preparation method, during step S2, stirring may be performed during the mixing of the carbon black acetylation reagent and the cuprous salt, and stirring may also be performed during the activation treatment. The stirring speed is 60-600 rpm, for example, but not limited to, specific values ​​such as 60 rpm, 120 rpm, 240 rpm, 360 rpm, 480 rpm, 600 rpm, etc., and a range with any two of the above specific values ​​as endpoints.

[0037] In the above preparation method, the order of adding each reagent in the activation treatment of S2 can be as follows: first add the second solvent, then add the carbon black acetylation reagent, and then add the cuprous salt.

[0038] In the above preparation method, the product of the activation treatment can undergo post-processing, such as sequential filtration, washing, and vacuum drying, before being used for carbon black acetylation treatment. The filtration is carried out in a protective atmosphere, which may specifically include a nitrogen atmosphere and / or an argon atmosphere; the filtration uses any suction filtration device, with the filter medium preferably being a G4 sand core funnel and / or a G5 sand core funnel covered with medium-speed filter paper. The washing can use a dry aprotic solvent to rinse the filter residue, preferably the same solvent as the second solvent used in the activation treatment, and the rinsing amount is preferably 2-3 times the amount of solvent used in the halogenation treatment, for example, but not limited to specific values ​​such as 2 times, 2.5 times, 3 times, etc., and a range with any two of the above specific values ​​as endpoints. The vacuum drying is the removal of residual solvent inside the filter residue under vacuum conditions. The vacuum drying temperature can be 50-150℃, for example, but not limited to specific values ​​such as 50℃, 70℃, 80℃, 110℃, 130℃, 150℃, etc., and any two of the above specific values ​​as endpoints; the vacuum drying time is 12-24h, for example, but not limited to specific values ​​such as 12h, 18h, 24h, etc., and any two of the above specific values ​​as endpoints.

[0039] In the above preparation method, in S2, the activation efficiency of the acetylation reagent can be adjusted by controlling the type of cuprous salt and the ratio of the acetylation reagent to the cuprous salt.

[0040] In the above preparation method, in step S3, the carbon black acetylation process uses a main catalyst for catalysis. The main catalyst may specifically include a palladium-based catalyst, which may include one or more of the following: palladium trifluoroacetate, palladium acetate, tetra-triphenylphosphine palladium, dichlorobis(triphenylphosphine)palladium, [bis(diphenylphosphine)ferrocene]palladium dichloride, bis(acetonitrile)palladium dichloride, bis(tricyclohexylphosphine)palladium dichloride, hexafluoroacetylacetone palladium, (1,5-cyclooctadiene)palladium dichloride, bis(dibenzylacetone)palladium, [1,2-bis(diphenylphosphine)ethane]palladium dichloride, dichlorobis(tri-o-toluene)palladium, (2,2'-bipyridine)palladium dichloride, di(cyanobenzene)palladium dichloride, and bis(diphenylacetone)palladium.

[0041] In the above preparation method, in step S3, the carbon black acetylation process can also be catalyzed using a co-catalyst, which includes a phosphorus-containing compound. Specifically, the phosphorus-containing compound may include one or a combination of two or more of the following: triphenylphosphine, tricyclohexylphosphine, 2-di-tert-butylphosphine-1-phenylindole, 1,3-bis(diphenylphosphine)propane, 1,4-bis(diphenylphosphine)butane, tri-tert-butylphosphine, n-butylbis(1-adamantyl)phosphine, tris(2-furanyl)phosphine, and 2-tert-butylphosphine-1-phenylindole.

[0042] In the above preparation method, in S3, the molar ratio of the main catalyst to the co-catalyst used in the carbon black acetylation treatment can be controlled to be 1:(1-4), for example, but not limited to specific values ​​such as 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, and any two of the above specific values ​​as endpoints.

[0043] In the above preparation method, in S3, the mass ratio of the total mass of the main catalyst and the co-catalyst to the mass of the conductive carbon black precursor during the carbon black acetylation treatment can be 1:(50-230) (that is, the mass ratio of the conductive carbon black precursor to the molar amount of the activated acetylation reagent can be 1 kg:(0.07-1.5) mol), for example, but not limited to specific values ​​such as 1:50, 1:60, 1:70, 1:80, 1:90, 1:100, 1:130, 1:170, 1:200, 1:230, and any two of the above specific values ​​as endpoints.

[0044] In the above preparation method, in S3, the activated acetylation reagent and the conductive carbon black precursor can be mixed in a third solvent to form an acetylation raw material solution, and then carbon black acetylation treatment is performed.

[0045] In the above preparation method, in step S3, the third solvent can be a combination of an aprotic solvent and an organic tertiary amine. The aprotic solvent can include one or more of tetrahydrofuran, dioxane, dichloromethane, acetonitrile, dimethyl sulfoxide, and N,N-dimethylformamide; the organic tertiary amine can include one or more of triethylamine, dicyclohexylmethylamine, tripropylamine, triargylpropylamine, triallylamine, tetraethylethylenediamine, 1,4-diethylpiperazine, 1-ethylpyrrolidine, 1-butylpyrrolidine, tripentylamine, N-ethylpiperidine, and N,N-dimethylformamide.

[0046] In the above preparation method, the volume ratio of the aprotic solvent to the organic tertiary amine in the third solvent can be 1:(0.05-0.33), for example, but not limited to specific values ​​such as 1:0.05, 1:0.1, 1:0.2, 1:0.25, 1:0.3, 1:0.33, etc., and a range with any two of the above specific values ​​as endpoints.

[0047] In the above preparation method, in S3, during the carbon black acetylation treatment, the ratio of the kilogram of the conductive carbon black precursor to the molar amount of the activated acetylation reagent can be controlled to be 1:(0.07-1.5) (that is, the ratio of the mass of the conductive carbon black precursor to the molar amount of the activated acetylation reagent is 1 kg:(0.07-1.5) mol), for example, but not limited to specific values ​​such as 1:0.07, 1:0.1, 1:0.2, 1:0.3, 1:0.5, 1:0.7, 1:1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, etc., and the range with any two of the above specific values ​​as endpoints.

[0048] In the above preparation method, the mass percentage of the conductive carbon black precursor in the acetylation raw material solution (also known as the total reaction system) during the carbon black acetylation treatment can be 10%-28%, for example, but not limited to specific values ​​such as 10%, 19%, 23%, 25%, 28%, etc., and a range with any two of the above specific values ​​as endpoints.

[0049] In the above preparation method, the carbon black acetylation treatment is carried out in a protective atmosphere, which may include a nitrogen atmosphere and / or an argon atmosphere.

[0050] In the above preparation method, the aprotic solvent and the organic tertiary amine in the third solvent can be dried before use so that the water content of the aprotic solvent and the organic tertiary amine is not higher than 50 ppm.

[0051] In the above preparation method, the temperature of the carbon black acetylation treatment can be controlled to be 50-180℃, for example, but not limited to specific values ​​such as 50℃, 70℃, 90℃, 110℃, 150℃, etc., and a range with any two of the above specific values ​​as endpoints.

[0052] In the above preparation method, the carbon black acetylation treatment time can be controlled to be 6h-24h, for example, but not limited to specific values ​​such as 6h, 12h, 18h, 24h, and any two of the above specific values ​​as endpoints.

[0053] In the above preparation method, during step S3, stirring may be performed during the mixing of the activated acetylation reagent and the carbon black precursor, and stirring may also be performed during the carbon black acetylation treatment. The stirring speed can be controlled to be 120-600 rpm, for example, but not limited to specific values ​​such as 120 rpm, 240 rpm, 360 rpm, 480 rpm, and 600 rpm, as well as a range with any two of the above specific values ​​as endpoints.

[0054] In the above preparation method, the order of adding each reagent in the carbon black acetylation treatment of S3 is as follows: add aprotic solvent, organic tertiary amine, main catalyst, co-catalyst, conductive carbon black precursor, and activated acetylation reagent in sequence.

[0055] In the above preparation method, the product of the carbon black acetylation treatment can undergo post-processing, such as sequential filtration, washing, and vacuum drying, before being used for deprotection treatment. The filtration is carried out in a protective atmosphere, which may include a nitrogen atmosphere and / or an argon atmosphere; the filtration uses any suction filtration device, and the filter medium may include a G4 sand core funnel and / or a G5 sand core funnel covered with medium-speed filter paper. The washing can use a first rinsing solvent and a second rinsing solvent to wash the filter residue sequentially; the first rinsing solvent is preferably the same solvent used in the carbon black acetylation treatment; the amount of the first rinsing solvent can be 2-3 times the total amount of solvent used in the carbon black acetylation treatment (the total amount of the third solvent), for example, but not limited to 2 times, 2.5 times, 3 times, etc., and any two of the above specific values ​​as endpoints; the second rinsing solvent can be a strongly polar solvent, such as deionized water; the amount of the second rinsing solvent can be 1-2 times the total amount of solvent used in the carbon black acetylation treatment, for example, but not limited to 1 time, 1.5 times, 2 times, etc., and any two of the above specific values ​​as endpoints. The vacuum drying temperature can be 50-220℃, for example, but not limited to specific values ​​such as 50℃, 70℃, 90℃, 100℃, 130℃, 150℃, etc., and the range with any two of the above specific values ​​as endpoints. The vacuum drying time can be 12h-24h, for example, but not limited to specific values ​​such as 12h, 18h, 24h, etc., and the range with any two of the above specific values ​​as endpoints.

[0056] In the above preparation method, the activity of the reaction system can be adjusted by controlling the type of palladium catalyst, the type of co-catalyst, the type of organic tertiary amine, and the amounts of palladium catalyst, co-catalyst, and organic tertiary amine in the carbon black acetylation treatment of S3.

[0057] In the above preparation method, S3, the deprotection treatment includes: mixing the conductive carbon black pressed product with an alkaline solution for deprotection treatment to obtain the conductive carbon black finished product.

[0058] In the above preparation method, the pH value of the alkaline solution used in the deprotection treatment is generally greater than or equal to 7.5. The solute in the alkaline solution may include organic alkaline substances and / or inorganic alkaline substances, including but not limited to one or more combinations of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium phosphate, potassium phosphate, sodium sulfide, sodium thiosulfate, sodium acetate, and potassium acetate. The solvent of the alkaline solution may be a protic solvent, specifically including but not limited to one or more combinations of water, methanol, ethanol, propanol, isopropanol, butanol, ethylenediamine, diethylamine, propylamine, dibutylamine, and diisopropylamine.

[0059] In the above preparation method, the concentration of the alkaline solution in the deprotection treatment can be controlled to be 0.5-2.5 mol / L, for example, but not limited to specific values ​​such as 0.5 mol / L, 0.75 mol / L, 0.8 mol / L, 1 mol / L, 1.25 mol / L, 1.33 mol / L, 1.5 mol / L, 2.5 mol / L, etc., and a range with any two of the above specific values ​​as endpoints.

[0060] In the above preparation method, the mass ratio of the deprotected conductive carbon black sub-finished product to the alkaline solution can be controlled to be 1:(1.5-10), for example, but not limited to specific values ​​such as 1:1.5, 1:2, 1:3, 1:4, 1:5.5, 1:7, 1:8, 1:9, 1:10, and any two of the above specific values ​​as endpoints.

[0061] In the above preparation method, the deprotection treatment temperature can be controlled between 25-100℃, for example, but not limited to specific values ​​such as 25℃, 50℃, 70℃, 85℃, and 100℃, and a range with any two of the above specific values ​​as endpoints. The deprotection treatment time can be controlled between 12h-48h, for example, but not limited to specific values ​​such as 12h, 18h, 24h, and 48h, and a range with any two of the above specific values ​​as endpoints.

[0062] In the above preparation method, stirring can be performed during the deprotection treatment. The stirring rate can be 60-300 rpm, for example, but not limited to specific values ​​such as 60 rpm, 120 rpm, 180 rpm, 240 rpm, 300 rpm, etc., and a range with any two of the above specific values ​​as endpoints.

[0063] In the above preparation method, during the deprotection treatment of S3, the order of adding the reagents can be as follows: alkaline solution, carbon black sub-product.

[0064] In the above preparation method, the product of the deprotection treatment can be post-processed, such as sequentially filtered, washed, and vacuum dried, before being used in battery preparation. The filtration uses any suction filtration device, and the filter medium can include a G4 sintered sand funnel and / or a G5 sintered sand funnel covered with medium-speed filter paper. The washing can use a third rinsing solvent and a fourth rinsing solvent to wash the filter residue sequentially; the third rinsing solvent can specifically include one or more combinations of dichloromethane, petroleum ether, tetrahydrofuran, and toluene; the amount of the third rinsing solvent can be 1-1.5 times the amount of alkaline solution used in the carbon black deprotection treatment, for example, but not limited to 1 time, 1.5 times, etc.; the fourth rinsing solvent can be a strongly polar solvent, such as deionized water; the amount of the fourth rinsing solvent can be 1-2 times the amount of solvent used in the carbon black acetylation treatment (i.e., the amount of solvent in the alkaline solution), for example, but not limited to specific values ​​such as 1 time, 1.5 times, 2 times, etc., and a range with any two of the above specific values ​​as endpoints. The vacuum drying temperature can be 50-100℃, for example, but not limited to specific values ​​such as 50℃, 70℃, 90℃, 100℃, etc., and the range with any two of the above specific values ​​as endpoints. The vacuum drying time can be 12h-24h, for example, but not limited to specific values ​​such as 12h, 18h, 24h, etc., and the range with any two of the above specific values ​​as endpoints.

[0065] According to a specific embodiment of the present invention, the method for preparing the above-mentioned conductive carbon black may specifically include:

[0066] 1. Add raw carbon black (dried at 70-160℃ for 6-24h) and halogenating reagent sequentially to the first solvent (dried to a water content of less than or equal to 50ppm), and stir at 60-720rpm to form a halogenated raw material solution; wherein, the molar ratio of the mass of raw carbon black to the molar mass of halogen atoms in the halogenating reagent is 1kg:(0.1-0.67)mol, and the mass of raw carbon black is 10%-25% of the total mass of the halogenated raw material solution (i.e., the total mass of raw carbon black, halogenating reagent, and solvent);

[0067] Keep stirring and halogenate at 25-125℃ for 12-48h in a protective atmosphere. Filter the halogenated product in a protective atmosphere, wash the filter residue with a dry aprotic solvent, and vacuum dry at 50-130℃ for 12-24h to obtain the conductive carbon black precursor.

[0068] 2. Add carbon black acetylation reagent and cuprous salt to the second solvent in sequence, and stir and mix at 60-600 rpm to form an activated raw material solution; wherein, the molar ratio of carbon black acetylation reagent to cuprous salt is 1:(1.05-1.4), and the total concentration of carbon black acetylation reagent and cuprous salt in the activated raw material solution is 0.15-2 mol / L;

[0069] Keep stirring and activate the product at 25-100℃ for 24-48h in a protective atmosphere. Filter the activated product in a protective atmosphere, wash the filter residue with a dry aprotic solvent, and vacuum dry at 50-150℃ for 12-24h to obtain the activated acetylation reagent.

[0070] 3. A third solvent is formed by mixing a dried aprotic solvent with a water content of no more than 50 ppm with an organic tertiary amine at a volume ratio of 1:(0.05-0.33). The main catalyst, co-catalyst, conductive carbon black precursor and activated acetylation reagent are added to the third solvent in sequence and stirred at 120-600 rpm to form a reaction system.

[0071] The ratio of the number of kilograms of conductive carbon black precursor to the number of moles of activated acetylation reagent is 1 kg: (0.07-1.5) mol, the mass percentage of conductive carbon black precursor in the reaction system is 10%-28%, the mass ratio of the total mass of the main catalyst and the co-catalyst to the mass of the conductive carbon black precursor is 1: (50-230), and the molar ratio of the main catalyst to the co-catalyst is 1: (1-4).

[0072] Keep stirring and carry out carbon black acetylation treatment at 50-180℃ for 6-24h in a protective atmosphere. Filter the carbon black acetylation treatment product in a protective atmosphere, wash the filter residue, and vacuum dry at 50-220℃ for 12h-24h to obtain conductive carbon black sub-product.

[0073] 4. Mix the conductive carbon black sub-finished product with an alkaline solution of pH ≥ 7.5 and a concentration of 0.5-2.5 mol / L. Stir at a speed of 60-300 rpm. The mass ratio of the conductive carbon black sub-finished product to the alkaline solution is 1:(1.5-7).

[0074] Keep stirring and perform deprotection treatment at 25-100℃ for 12-48 hours. Filter, wash and vacuum dry at 50-100℃ for 12-24 hours to obtain conductive carbon black.

[0075] The present invention also provides a conductive carbon black, which is obtained by the above preparation method.

[0076] According to a specific embodiment of the present invention, the specific surface area of ​​the conductive carbon black can be 120-560 m². 2 / g, for example, but not limited to 122m 2 / g、146m 2 / g、182m 2 / g、211m 2 / g、242m 2 / g、253m 2 / g、277m 2 / g、315m2 / g、344m 2 / g、375m 2 / g、433m 2 / g、455m 2 / g、508m 2 / g、556m 2 The specific values ​​such as / g and the range with any two of the above specific values ​​as endpoints.

[0077] According to a specific embodiment of the present invention, the oil absorption value of the conductive carbon black is 120-330cc / 100g, for example, but not limited to, specific values ​​such as 127cc / 100g, 155cc / 100g, 174cc / 100g, 198cc / 100g, 219cc / 100g, 227cc / 100g, 245cc / 100g, 246cc / 100g, 255cc / 100g, 279cc / 100g, 289cc / 100g, 311cc / 100g, 327cc / 100g, etc., and a range with any two of the above specific values ​​as endpoints.

[0078] According to a specific embodiment of the present invention, the degree of graphitization of the conductive carbon black is 20%-42%, for example, but not limited to, specific values ​​such as 20.5%, 23.5%, 24.6%, 25.8%, 25.9%, 26.2%, 26.4%, 27.0%, 28.6%, 30.3%, 30.9%, 32.3%, 33.5%, 35.3%, 41.7%, etc., and a range with any two of the above specific values ​​as endpoints.

[0079] According to a specific embodiment of the present invention, the alkynyl content in the conductive carbon black is 30-500 mmol / kg carbon black (i.e., 1 kg of conductive carbon black includes 30-500 mmol of alkynyl groups), for example, but not limited to, specific values ​​such as 36 mmol / kg carbon black, 61 mmol / kg carbon black, 77 mmol / kg carbon black, 123 mmol / kg carbon black, 129 mmol / kg carbon black, 164 mmol / kg carbon black, 186 mmol / kg carbon black, 269 mmol / kg carbon black, 279 mmol / kg carbon black, 352 mmol / kg carbon black, 366 mmol / kg carbon black, 404 mmol / kg carbon black, 451 mmol / kg carbon black, 498 mmol / kg carbon black, etc., and a range with any two of the above specific values ​​as endpoints.

[0080] According to a specific embodiment of the present invention, the acetylene group content in the conductive carbon black is 0.2-1.4 μmol / m 2 Carbon black (i.e., 1m) 2Conductive carbon black includes 0.2-1.4 μmol acetylinyl groups, for example, but not limited to 0.289 μmol / m 2 Carbon black, 0.295 μmol / m 2 Carbon black, 0.496 μmol / m 2 Carbon black, 0.531 μmol / m 2 Carbon black, 0.533 μmol / m 2 Carbon black, 0.621 μmol / m 2 Carbon black, 0.646 μmol / m 2 Carbon black, 0.672 μmol / m 2 Carbon black, 0.774 μmol / m 2 Carbon black, 0.792 μmol / m 2 Carbon black, 0.884 μmol / m 2 Carbon black, 1.004 μmol / m 2 Carbon black, 1.162 μmol / m 2 Carbon black, 1.315 μmol / m 2 Specific values ​​for carbon black, etc., and the range with any two of the above specific values ​​as endpoints.

[0081] The present invention also provides a lithium battery, the raw material of which includes the above-mentioned conductive carbon black. The lithium battery made using the conductive carbon black of the present invention has a long cycle life.

[0082] According to a specific embodiment of the present invention, the lithium battery generally includes a positive electrode, a negative electrode, and an ion transport medium. The positive electrode is made of a positive electrode active material, a conductive agent, and a binder; the negative electrode is made of a negative electrode active material, a conductive agent, and a binder.

[0083] The lithium battery described in this invention refers to an energy storage device that stores and releases energy by means of lithium ions shuttling between the positive and negative electrode active materials. The lithium battery includes, but is not limited to, one or more combinations of liquid lithium-ion batteries, semi-solid lithium-ion batteries, all-solid lithium-ion batteries, lithium-sulfur batteries, and lithium-oxygen batteries.

[0084] According to a specific embodiment of the present invention, the positive electrode active material of the above-mentioned lithium battery includes, but is not limited to, nickel-cobalt-manganese ternary positive electrode material (LiNi). x Co y Mn z O2, where x+y+z=1, and the ratio of x, y, z includes, but is not limited to, specific values ​​such as 1:1:1, 4:2:4, 5:2:3, 6:2:2, 7:1:2, 8:1:1, 9:0.5:0.5, and ranges with any two of the above specific values ​​as endpoints), nickel-cobalt-aluminum ternary cathode material (LiNi x Co y Alz O2, where x+y+z=1, and the ratio of x, y, z includes, but is not limited to, specific values ​​such as 8:1.5:0.5, 8.5:1.2:0.3, and ranges with any two of the above specific values ​​as endpoints), lithium-rich manganese-based cathode materials (Li2MnO3), lithium iron phosphate (LiFePO4), and lithium manganese iron phosphate (LiMn x Fe y PO4, where x+y=1, and the ratio of x to y includes, but is not limited to, specific values ​​such as 1:1, 6:4, 4:6, and ranges with any two of the above specific values ​​as endpoints; single crystals or polycrystalline forms of lithium cobalt oxide (LiCoO2), lithium manganese oxide (LiMn2O4), and lithium nickel oxide (LiNiO2); positive electrode active materials obtained by modifying the above materials through doping; and positive electrode active materials obtained by coating the above materials.

[0085] According to a specific embodiment of the present invention, the conductive agent in the positive electrode of the lithium battery includes the conductive carbon black provided by the present invention; it may further include one or more combinations of carbon nanotubes and graphene. Specifically, the carbon nanotubes may include single-walled carbon nanotubes and / or multi-walled carbon nanotubes.

[0086] According to a specific embodiment of the present invention, the binder in the positive electrode of the lithium battery includes one or a combination of two or more of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polymethyl methacrylate (PMMA), sodium alginate (SA), polyvinyl alcohol (PVA), hydrogenated nitrile butadiene rubber (HNBR), and polyacrylic acid (PAA).

[0087] According to a specific embodiment of the present invention, the negative electrode active material of the lithium battery includes, but is not limited to, one or more combinations of artificial graphite, natural graphite, soft carbon, hard carbon, silicon-carbon negative electrode material, silicon-oxygen negative electrode material, elemental lithium, lithium-tin alloy, elemental sulfur, titanium disulfide (TiS2), molybdenum disulfide (MoS2), elemental oxygen, and graphite / SiO.

[0088] According to a specific embodiment of the present invention, the conductive agent in the negative electrode of the lithium battery includes one or more of conductive carbon black, carbon nanotubes, and graphene. Specifically, the carbon nanotubes may include single-walled carbon nanotubes and / or multi-walled carbon nanotubes.

[0089] According to a specific embodiment of the present invention, the binder in the negative electrode of the lithium battery includes one or a combination of two or more of styrene-butadiene rubber (SBR), sodium alginate (SA), polyvinyl alcohol (PVA), and polyacrylic acid (PAA).

[0090] According to a specific embodiment of the present invention, the negative electrode may further include a thickener, which may specifically include carboxymethyl cellulose (CMC).

[0091] According to specific embodiments of the present invention, the conductive carbon black provided by the present invention is applicable to any type of ion transport medium. For example, the ion transport medium includes, but is not limited to, one or more combinations of electrolytes, polymer gel electrolytes, and solid electrolytes.

[0092] According to a specific embodiment of the present invention, the electrolyte contains a lithium salt and a solvent. The lithium salt includes, but is not limited to, one or more combinations of lithium chloride (LiCl), lithium perchlorate (LiClO4), lithium tetrafluoroborate (LiBF4), lithium hexafluorophosphate (LiPF6), lithium hexafluoroarsenate (LiAsF6), lithium bis(oxalato)borate (LiBC4O8), lithium bis(trifluoromethanesulfonate)imide (LiC2S2O4NF6), and lithium nitrate (LiNO3). The solvent of the electrolyte includes, but is not limited to, one or more combinations of ethyl methyl carbonate (EMC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylene carbonate (EC), fluoroethylene carbonate (FEC), chloroethylene carbonate (CEC), propylene carbonate (PC), and trifluoromethyl ethylene carbonate (TFEC).

[0093] According to a specific embodiment of the present invention, the gel polymer electrolyte comprises a polymer, which includes one or more of polyvinylidene fluoride (PVDF), polyethylene oxide (PEO), polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), and vinylidene fluoride-hexafluoropropylene copolymer (PVDFHFP).

[0094] According to a specific embodiment of the present invention, the solid electrolyte includes one or more of lithium lanthanum zirconium oxide (LLZO), lithium lanthanum titanium oxide (LLTO), lithium phosphorus sulfide chloride (LPSCl), lithium phosphorus sulfide (LPS), and lithium germanium phosphorus sulfide (LGPS).

[0095] According to a specific embodiment of the present invention, the lithium battery further includes a separator. The conductive carbon black provided by the present invention is applicable to any type of separator. For example, the separator may include a resin-based separator, the resin-based separator comprising a substrate and a coating coated on the surface of the substrate, the substrate comprising one or more of polyethylene, polypropylene, and polyimide, and the coating comprising an alumina thermal shock resistant layer and / or a boehmite thermal alluvial resistant layer.

[0096] In this invention, the specific surface area (BET) of conductive carbon black refers to the total specific surface area of ​​carbon black obtained by nitrogen adsorption measurement, reflecting the average particle size of the primary particles constituting the carbon black. The detection method is based on document ASTM D6556-10. The oil absorption value (OAN) of conductive carbon black in this invention refers to the volume of organic liquid that 100 grams of carbon black can absorb, reflecting the microscopic growth characteristics of carbon black particles. The detection method is based on document ASTM D2414-13a. The degree of graphitization of conductive carbon black in this invention reflects the degree of microscopic order of the carbon black. The detection method is based on the literature Carbon. 1994.32, 1377-1382, "Ramanstudies of heat-treated carbon blacks". The metal element content of conductive carbon black in this invention is closely related to battery side reactions and internal short circuits. The detection method is based on document ASTM D8371-24. The sulfur content of conductive carbon black in this invention is detected according to document ASTM D1619-20. The quantitative infrared spectroscopy method for determining the acetylene content of conductive carbon black described in this invention is based on document ASTM E168-06. The solvent moisture determination method described in this invention is based on document ASTM E1064-16. Lithium battery performance testing, such as room temperature discharge capacity, low temperature discharge capacity, room temperature high rate discharge capacity, cycle durability, DC internal resistance, etc., is based on document IEC 61960.

[0097] The beneficial effects of this invention include:

[0098] 1. The alkynyl functionalization of conductive carbon black surface provided by the present invention can undergo alkynyl coupling reaction during the lithium battery formation stage, so as to form a strong conjugated and covalent bond connection between carbon black particles. On the one hand, it improves the electron transport performance inside the electrode, and on the other hand, it improves the stability of the battery electrode structure, thereby extending the cycle life of the battery. Therefore, it is of great significance to the continued rapid development of the lithium battery industry.

[0099] 2. The conductive carbon black produced by the method of this invention, when applied to lithium batteries, can significantly improve the cycle life of the battery by more than 30% without affecting parameters such as room temperature discharge capacity, low temperature discharge capacity, and high-rate discharge capacity at room temperature. Furthermore, this improvement in lithium battery cycle life is universally applicable to carbon black raw materials and battery materials with different properties. Attached Figure Description

[0100] Figure 1 It represents the initial discharge capacity of the battery cells made from conductive carbon black and raw material carbon black in each embodiment under room temperature conditions.

[0101] Figure 2 The discharge capacity of the battery cells made from conductive carbon black and raw material carbon black in each embodiment under low temperature (-20℃) conditions.

[0102] Figure 3 It is the discharge capacity of the battery cells made from conductive carbon black and raw material carbon black in each embodiment at 1C under room temperature conditions.

[0103] Figure 4 The number of cycles is the number of battery cells made from conductive carbon black and raw material carbon black in each embodiment at room temperature when the discharge capacity remains at 70%.

[0104] Figure 5 It is the DC internal resistance of the battery cells made from conductive carbon black and raw material carbon black in each embodiment under room temperature conditions in their initial state.

[0105] Figure 6 It is the DC internal resistance of the battery cells made from conductive carbon black and raw material carbon black in each embodiment after 750 cycles at room temperature. Detailed Implementation

[0106] In order to provide a clearer understanding of the technical features, objectives and beneficial effects of the present invention, the technical solution of the present invention will now be described in detail below, but it should not be construed as limiting the scope of implementation of the present invention.

[0107] The following describes the preparation method and product of conductive carbon black for long-cycle-life lithium batteries, as well as the performance of this product in lithium batteries. The measured parameters of the raw carbon black used in the examples are listed in Table 1. In Table 1, OAN represents the oil absorption value, BET represents the specific surface area, and the content of the six metals refers to the content of six metallic elements: nickel, cobalt, manganese, zinc, copper, and chromium.

[0108] Table 1

[0109]

[0110]

[0111] The measured indicators of the conductive carbon black products obtained in the examples are listed in Table 2.

[0112] Table 2

[0113]

[0114] The electrolyte used for battery performance testing in the pouch cell was a 1 mol / L lithium hexafluorophosphate electrolyte produced by Sigma-Aldrich, and the solvent was a 1:1 volume ratio mixture of ethylene carbonate and diethyl carbonate; the separator was... Type 2325 PP / PE / PP three-layer composite membrane, 25 microns thick.

[0115] The formulations of the pouch cells used for battery performance testing are listed in Tables 3-8. Among them, carbon nanotubes are commercially available products with a diameter of 5-15 nanometers, and graphite / SiO is a commercially available product with an 8% SiO content by mass. All pouch cells have a nominal capacity of 1.5 Ah. The nickel-cobalt-manganese 811 is a LiNi alloy with an x, y, z ratio of 8:1:1. x Co y Mn z O2 cathode material; LiNi with nickel-cobalt-manganese 111 where x+y+z=1 and the ratio of x, y, z is 1:1:1. x Co y Mn z O2 cathode material; Nickel-Cobalt-Manganese 424 is a LiNi alloy where x+y+z=1 and the ratio of x, y, z is 4:2:4. x Co y Mn z O2 cathode material. Lithium manganese iron phosphate (LiMn) x Fe y In PO4), x + y = 1, and the ratio of x to y is 1:1. The graphite used in formulas three, four, five, and six is ​​all artificial graphite.

[0116] Table 3

[0117]

[0118] Table 4

[0119]

[0120] Table 5

[0121]

[0122] Table 6

[0123]

[0124]

[0125] Table 7

[0126]

[0127] Table 8

[0128]

[0129] Example 1

[0130] This embodiment provides a conductive carbon black, the preparation method of which includes:

[0131] A 500 mL round-bottom flask equipped with a magnetic stirrer was transferred to an argon-atmosphere glove box and fixed on a heated magnetic stirring table. 226 mL of dried dichloromethane with a water content of 23 ppm was added to the round-bottom flask. 100 g of raw carbon black 1, dried at 70°C for 6 h, was added to the round-bottom flask. The stirrer was started at 60 rpm. The temperature was maintained within the range of 25 ± 1°C. After five minutes, 0.812 g of iodine chloride was added dropwise to the round-bottom flask using a syringe. In this embodiment, the ratio of the weight of raw carbon black 1 to the molar number of halogen atoms in iodine chloride was 1:0.1, and the raw carbon black accounted for 25% of the total mass of raw carbon black, halogenating reagent, and solvent. After the halogenating reagent was added, the temperature and stirring speed were maintained, and stirring continued for 24 h. After the reaction was completed, the mixture was filtered using a vacuum filtration flask in a glove box. All the material in the round-bottom flask was slowly poured into a G4 sintered glass funnel lined with medium-speed filter paper. The filter residue was washed three times with 452 mL of dichloromethane. The filter residue, along with the funnel, was transferred to a vacuum drying oven and dried at 50°C for 12 hours to obtain conductive carbon black precursor 1.

[0132] A 500 mL round-bottom flask equipped with a magnetic stirrer was transferred to an argon-atmosphere glove box and fixed on a heated magnetic stirring table. 120 mL of dried dimethyl sulfoxide (DMSO) with a water content of 37 ppm was added to the round-bottom flask. 28.443 g of triphenylsilylacetylene was added to the round-bottom flask. The stirrer was started at 60 rpm. The temperature was maintained at 25 ± 1 °C. After five minutes, 26.663 g of cuprous iodide was added to the round-bottom flask. In this example, the molar ratio of carbon black acetylation reagent to cuprous salt was 1:1.4, and the total concentration of carbon black acetylation reagent and cuprous salt in the solution was 2 mol / L. After the cuprous iodide was added, the temperature was raised to 100 °C and stirring was continued for 24 hours. After the reaction was completed, the mixture was filtered using a vacuum filtration flask in a glove box filled with a protective atmosphere. All the material in the round-bottom flask was slowly poured into a G4 sintered glass funnel lined with medium-speed filter paper. The filter residue was washed three times with 360 mL of dimethyl sulfoxide. The filter residue, along with the funnel, was transferred to a vacuum drying oven and dried at 150°C for 24 hours to obtain activated acetylation reagent 1.

[0133] Transfer a 500 mL round-bottom flask equipped with a magnetic stirrer to an argon-atmosphere glove box and secure it to a heated magnetic stirring table. Add 275 mL of dried tetrahydrofuran with a water content of 42 ppm to the round-bottom flask. Add 14 mL of dried triethylamine with a water content of 33 ppm to the round-bottom flask. Add 0.201 g of palladium acetate and 0.234 g of triphenylphosphine to the round-bottom flask. Start the stirrer at 120 rpm. Maintain the temperature within the range of 25 ± 1 °C. After three minutes, add 100 g of conductive carbon black precursor 1 to the round-bottom flask. Add 2.429 g of activated acetylation reagent 1 to the round-bottom flask. In this embodiment, the volume ratio of the aprotic solvent to the organic tertiary amine is 1:0.05, the molar ratio of the catalyst to the co-catalyst is 1:1, the ratio of the kilogram of the conductive carbon black precursor to the molar amount of the activated acetylation reagent is 1:0.07, the total mass ratio of the catalyst and co-catalyst to the conductive carbon black precursor is 1:230, and the mass percentage of the conductive carbon black precursor in the total reaction system is 28%. After the activated acetylation reagent is added, the temperature is raised to 50°C and stirred continuously for 12 hours. After the reaction is completed, the mixture is filtered in a glove box using a vacuum filtration flask. All the material in the round-bottom flask is slowly poured into a G4 sintered glass funnel covered with medium-speed filter paper. The filter residue is washed twice with 578 mL of tetrahydrofuran, and then washed three times with 289 mL of deionized water. The filter residue, along with the funnel, is transferred to a vacuum drying oven and dried at 50°C for 12 hours to obtain conductive carbon black sub-product 1.

[0134] A 1L round-bottom flask equipped with a magnetic stirrer was fixed on a magnetic stirring table with heating function. 400g of a 1.5mol / L sodium hydroxide aqueous solution was added to the round-bottom flask. The stirrer was started at 60rpm. The temperature was maintained within the range of 25±1℃. 100g of conductive carbon black sub-product 1 was added to the round-bottom flask. The temperature was raised to 100℃ and the stirring speed was kept constant for 12 hours. After the reaction was completed, the mixture was filtered using a vacuum filtration flask. All the material in the round-bottom flask was slowly poured into a G4 sintered glass funnel covered with medium-speed filter paper. The filter residue was rinsed three times with 400mL of tetrahydrofuran, and then rinsed three times with 400mL of deionized water. The filter residue, along with the funnel, was transferred to a vacuum drying oven and dried at 50℃ for 12 hours to obtain conductive carbon black product 1.

[0135] This embodiment also provides a performance test experiment on the above-mentioned conductive carbon black finished product for soft-pack batteries. The test methods and results are as follows:

[0136] The conductive carbon black finished product 1 and the raw carbon black 1 were respectively assembled into 15 cells according to the soft-pack battery formula 1 for performance testing. Figure 1 This represents the initial discharge capacity of the battery cell at room temperature. Figure 2It is the discharge capacity of the battery cell under low temperature (-20℃) conditions; Figure 3 It is the discharge capacity of the cell at 1C under room temperature conditions; Figure 4 It is the number of cycles when the cell's discharge capacity remains at 70% under room temperature conditions; Figure 5 The DC internal resistance of the battery cell in its initial state at room temperature; Figure 6 This is the DC internal resistance of the battery cell after 750 cycles at room temperature. Three parallel samples were set up for each group of pouch cells: cell 1, cell 2, and cell 3. From... Figures 1 to 6 It can be seen that:

[0137] At 20℃, the average discharge capacity of the three 0.2C pouch cells based on conductive carbon black product 1 is 1.504 Ah, and the average DC internal resistance is 1.98 mΩ. The average discharge capacity of the three 0.2C pouch cells based on raw carbon black 1 is 1.505 Ah, and the average DC internal resistance is 1.99 mΩ. At -20℃, the average discharge capacity of the three 0.2C pouch cells based on conductive carbon black product 1 is 1.117 Ah, and the average discharge capacity of the three 0.2C pouch cells based on raw carbon black 1 is 1.112 Ah. At 20℃, the average discharge capacity of the three 1C pouch cells based on conductive carbon black product 1 is 1.418 Ah, and the average discharge capacity of the three 1C pouch cells based on raw carbon black 1 is 1.409 Ah.

[0138] At 20℃, after 1078, 1104, and 1092 charge-discharge cycles respectively, the discharge capacity retention rate of three pouch cells based on conductive carbon black product 1 decreased to 70%. Similarly, after 812, 788, and 803 charge-discharge cycles respectively, the discharge capacity retention rate of three pouch cells based on raw carbon black 1 decreased to 70%. The average cycle life of the cells based on conductive carbon black product 1 increased by 36.25% (calculated as: (sum of charge-discharge cycles of conductive carbon black / sum of charge-discharge cycles of raw carbon black - 1) × 100%). After 750 cycles, the average DC internal resistance of the cells based on conductive carbon black product 1 was 8.49 mΩ, while the average DC internal resistance of the cells based on raw carbon black 1 was 11.67 mΩ.

[0139] Example 2

[0140] This embodiment provides a conductive carbon black, the preparation method of which includes:

[0141] A 1L round-bottom flask equipped with a magnetic stirrer was transferred to an argon-atmosphere glove box and fixed on a heated magnetic stirring table. 506mL of dried hexane with a water content of 29ppm was added to the round-bottom flask. 100g of raw carbon black 2, dried at 70°C for 6 hours, was added to the round-bottom flask. The stirrer was started at 60rpm. The temperature was maintained within the range of 25±1°C. After five minutes, 1.624g of iodine chloride was slowly added to the round-bottom flask using a syringe. In this embodiment, the ratio of the weight of raw carbon black 2 to the molar number of halogen atoms in iodine chloride was 1:0.2, and the raw carbon black accounted for 23% of the total mass of raw carbon black, halogenating reagent, and solvent. After the halogenating reagent was added, the temperature was raised to 45°C and stirring was continued for 24 hours. After the reaction was completed, the mixture was filtered using a vacuum filtration flask in a glove box. All the material in the round-bottom flask was slowly poured into a G4 sintered glass funnel lined with medium-speed filter paper. The filter residue was washed three times with 1.264 L of n-hexane. The filter residue, along with the funnel, was transferred to a vacuum drying oven and dried at 50°C for 12 hours to obtain conductive carbon black precursor 2.

[0142] A 500 mL round-bottom flask equipped with a magnetic stirrer was transferred to an argon-atmosphere glove box and fixed on a heated magnetic stirring table. 126 mL of dried N,N-dimethylformamide with a water content of 35 ppm was added to the round-bottom flask. 16.029 g of dimethylphenylsilylacetylene was added to the round-bottom flask. The stirrer was started at 60 rpm. The temperature was maintained at 25 ± 1 °C. After five minutes, 26.663 g of cuprous iodide was added to the round-bottom flask. In this example, the molar ratio of carbon black acetylation reagent to cuprous salt was 1:1.4, and the total concentration of carbon black acetylation reagent and cuprous salt in the solution was 1.9 mol / L. After the cuprous iodide was added, the temperature was raised to 100 °C, and stirring was continued for 24 hours while maintaining the stirring speed. After the reaction was completed, the mixture was filtered using a vacuum filtration flask in a glove box. All the material in the round-bottom flask was slowly poured into a G4 sintered glass funnel lined with medium-speed filter paper. The filter residue was washed three times with 378 mL of N,N-dimethylformamide. The filter residue, along with the funnel, was transferred to a vacuum drying oven and dried at 130°C for 24 hours to obtain activated acetylation reagent 2.

[0143] Transfer a 500 mL round-bottom flask equipped with a magnetic stirrer to an argon-atmosphere glove box and secure it to a heated magnetic stirring table. Add 218 mL of dried dichloromethane with a water content of 23 ppm to the round-bottom flask. Add 11 mL of dried triethylamine with a water content of 33 ppm to the round-bottom flask. Add 0.229 g of palladium trifluoroacetate and 0.271 g of triphenylphosphine to the round-bottom flask. Start the stirrer at 120 rpm. Maintain the temperature within the range of 25 ± 1 °C. After three minutes, add 100 g of conductive carbon black precursor 2 to the round-bottom flask. Add 2.228 g of activated acetylation reagent 2 to the round-bottom flask. In this embodiment, the volume ratio of the aprotic solvent to the organic tertiary amine is 1:0.05, the molar ratio of the catalyst to the co-catalyst is 1:1.5, the ratio of the kilogram of the conductive carbon black precursor to the molar number of the activated acetylation reagent is 1:0.1, the total mass ratio of the catalyst and co-catalyst to the conductive carbon black precursor is 1:200, and the mass percentage of the conductive carbon black precursor in the total reaction system is 25%. After the activated acetylation reagent is added, the temperature is raised to 50°C and stirred continuously for 12 hours. After the reaction is completed, the mixture is filtered in a glove box using a vacuum filtration flask. All the material in the round-bottom flask is slowly poured into a G4 sintered glass funnel covered with medium-speed filter paper. The filter residue is washed twice with 458 mL of dichloromethane, and then washed three times with 229 mL of deionized water. The filter residue, along with the funnel, is transferred to a vacuum drying oven and dried at 50°C for 12 hours to obtain conductive carbon black sub-product 2.

[0144] A 1L round-bottom flask equipped with a magnetic stirrer was fixed on a magnetic stirring table with heating function. 400g of a 1.33mol / L potassium hydroxide aqueous solution was added to the round-bottom flask. The stirrer was started at 60rpm. The temperature was maintained within the range of 25±1℃. 100g of conductive carbon black sub-product 2 was added to the round-bottom flask. The temperature was raised to 100℃ and the stirring speed was kept constant for 12 hours. After the reaction was completed, the mixture was filtered using a vacuum filtration flask. All the material in the round-bottom flask was slowly poured into a G4 sintered glass funnel covered with medium-speed filter paper. The filter residue was rinsed three times with 400mL of tetrahydrofuran, and then rinsed three times with 400mL of deionized water. The filter residue, along with the funnel, was transferred to a vacuum drying oven and dried at 50℃ for 12 hours to obtain conductive carbon black product 2.

[0145] This embodiment also provides a performance test experiment on the above-mentioned conductive carbon black finished product for soft-pack batteries. The test methods and results are as follows:

[0146] Fifteen conductive carbon black finished product 2 and 15 raw carbon black 2 were assembled into cells according to the second formula for soft-pack batteries, respectively, for performance testing. The results are shown below. Figures 1 to 6 .

[0147] At 20℃, the average discharge capacity of the three 0.2C pouch cells based on conductive carbon black product 2 is 1.51Ah, and the average DC internal resistance is 1.96mΩ. The average discharge capacity of the three 0.2C pouch cells based on raw carbon black 2 is 1.508Ah, and the average DC internal resistance is 1.94mΩ. At -20℃, the average discharge capacity of the three 0.2C pouch cells based on conductive carbon black product 2 is 1.144Ah, and the average discharge capacity of the three 0.2C pouch cells based on raw carbon black 2 is 1.138Ah. At 20℃, the average discharge capacity of the three 1C pouch cells based on conductive carbon black product 2 is 1.438Ah, and the average discharge capacity of the three 1C pouch cells based on raw carbon black 2 is 1.435Ah.

[0148] At 20℃, after 1109, 1113, and 1119 charge-discharge cycles respectively, the discharge capacity retention rate of three pouch cells based on conductive carbon black product 2 decreased to 70%. After 824, 813, and 817 charge-discharge cycles respectively, the discharge capacity retention rate of three pouch cells based on raw carbon black 2 decreased to 70%. The average cycle life of the cells based on conductive carbon black product 2 increased by 36.15%. After 750 cycles, the average DC internal resistance of the cells based on conductive carbon black product 2 was 8.22 mΩ, while the average DC internal resistance of the cells based on raw carbon black 2 was 12.3 mΩ.

[0149] Example 3

[0150] This embodiment provides a conductive carbon black, the preparation method of which includes:

[0151] A 1L round-bottom flask equipped with a magnetic stirrer was transferred to an argon-atmosphere glove box and fixed on a heated magnetic stirring table. 426mL of dried cyclohexane with a water content of 31ppm was added to the round-bottom flask. 100g of raw carbon black 3, dried at 85°C for 6 hours, was added to the round-bottom flask. The stirrer was started at 60rpm. The temperature was maintained within the range of 25±1°C. After five minutes, 2.435g of iodine chloride was added dropwise to the round-bottom flask using a syringe. In this embodiment, the ratio of the weight of raw carbon black 3 to the molar number of halogen atoms in iodine chloride was 1:0.3, and the raw carbon black accounted for 23% of the total mass of raw carbon black, halogenating reagent, and solvent. After the halogenating reagent was added, the temperature was raised to 60°C and stirring was continued for 24 hours. After the reaction was completed, the mixture was filtered using a vacuum filtration flask in a glove box. All the material in the round-bottom flask was slowly poured into a G4 sintered glass funnel lined with medium-speed filter paper, and the filter residue was washed three times with 1.278 L of cyclohexane. The filter residue, along with the funnel, was transferred to a vacuum drying oven and dried at 50 °C for 12 h to obtain conductive carbon black precursor 3.

[0152] A 500 mL round-bottom flask equipped with a magnetic stirrer was transferred to an argon-atmosphere glove box and fixed on a heated magnetic stirring table. 133 mL of dried N-methylpyrrolidone with a water content of 40 ppm was added to the round-bottom flask. 18.238 g of triisopropylsilylacetylene was added to the round-bottom flask. The stirrer was started at 120 rpm. The temperature was maintained at 25 ± 1 °C. After five minutes, 26.663 g of cuprous iodide was added to the round-bottom flask. In this example, the molar ratio of carbon black acetylation reagent to cuprous salt was 1:1.4, and the total concentration of carbon black acetylation reagent and cuprous salt in the solution was 1.8 mol / L. After the cuprous iodide was added, the temperature was raised to 80 °C and stirring was continued for 36 hours. After the reaction was completed, the mixture was filtered using a vacuum filtration flask in a glove box. All the material in the round-bottom flask was slowly poured into a G4 sintered glass funnel lined with medium-speed filter paper. The filter residue was washed three times with 300 mL of N-methylpyrrolidone. The filter residue, along with the funnel, was transferred to a vacuum drying oven and dried at 110°C for 24 hours to obtain activated acetylation reagent 3.

[0153] Transfer a 1L round-bottom flask equipped with a magnetic stirrer to an argon-atmosphere glove box and secure it to a heated magnetic stirring table. Add 375mL of dried acetonitrile with a water content of 36ppm to the round-bottom flask. Add 37mL of dried triarginylamine with a water content of 45ppm to the round-bottom flask. Add 0.418g of (2,2'-bipyridine)palladium dichloride and 0.351g of tricyclohexylphosphine to the round-bottom flask. Start the stirrer at 240rpm. Maintain the temperature within the range of 25±1℃. After three minutes, add 100g of conductive carbon black precursor 3 to the round-bottom flask. Add 4.898g of activated acetylation reagent 3 to the round-bottom flask. In this embodiment, the volume ratio of the aprotic solvent to the organic tertiary amine is 1:0.1, the molar ratio of the catalyst to the co-catalyst is 1:1, the ratio of the kilogram of the conductive carbon black precursor to the molar amount of the activated acetylation reagent is 1:0.2, the total mass ratio of the catalyst and co-catalyst to the conductive carbon black precursor is 1:130, and the mass percentage of the conductive carbon black precursor in the total reaction system is 23%. After the activated acetylation reagent is added, the temperature is raised to 70°C and stirred continuously for 12 hours. After the reaction is completed, the mixture is filtered in a glove box using a vacuum filtration flask. All the material in the round-bottom flask is slowly poured into a G4 sintered glass funnel covered with medium-speed filter paper. The filter residue is washed twice with 824 mL of acetonitrile, and then washed three times with 618 mL of deionized water. The filter residue, along with the funnel, is transferred to a vacuum drying oven and dried at 70°C for 12 hours to obtain conductive carbon black sub-product 3.

[0154] A 1.5L round-bottom flask equipped with a magnetic stirrer was fixed on a magnetic stirring table with heating function. 550g of a 1.25mol / L sodium phosphate butanol solution was added to the round-bottom flask. The stirrer was started at 120rpm. The temperature was maintained within the range of 25±1℃. 100g of conductive carbon black sub-product 3 was added to the round-bottom flask. The temperature and stirring speed were maintained, and stirring continued for 24h. After the reaction was completed, the mixture was filtered using a vacuum filtration flask. All the material in the round-bottom flask was slowly poured into a G4 sintered glass funnel covered with medium-speed filter paper. The filter residue was washed three times with 679mL of tetrahydrofuran, and then washed three times with 679mL of deionized water. The filter residue, along with the funnel, was transferred to a vacuum drying oven and dried at 70℃ for 12h to obtain conductive carbon black product 3.

[0155] This embodiment also provides a performance test experiment on the above-mentioned conductive carbon black finished product for soft-pack batteries. The test methods and results are as follows:

[0156] Fifteen conductive carbon black products (3) and 15 raw carbon black products (3) were assembled into cells according to the third formula for soft-pack batteries for performance testing. The results are shown below. Figures 1 to 6 .

[0157] At 20℃, the average discharge capacity of the three 0.2C pouch cells based on conductive carbon black product 3 is 1.498 Ah, and the average DC internal resistance is 2 mΩ. The average discharge capacity of the three 0.2C pouch cells based on raw carbon black 3 is 1.508 Ah, and the average DC internal resistance is 1.98 mΩ. At -20℃, the average discharge capacity of the three 0.2C pouch cells based on conductive carbon black product 3 is 1.126 Ah, and the average discharge capacity of the three 0.2C pouch cells based on raw carbon black 3 is 1.122 Ah. At 20℃, the average discharge capacity of the three 1C pouch cells based on conductive carbon black product 3 is 1.424 Ah, and the average discharge capacity of the three 1C pouch cells based on raw carbon black 3 is 1.421 Ah.

[0158] At 20℃, after 1176, 1184, and 1172 charge-discharge cycles respectively, the discharge capacity retention rate of three pouch cells based on conductive carbon black product 3 decreased to 70%. After 831, 844, and 837 charge-discharge cycles respectively, the discharge capacity retention rate of three pouch cells based on raw carbon black 3 decreased to 70%. The average cycle life of the cells based on conductive carbon black product 3 increased by 40.61%. After 750 cycles, the average DC internal resistance of the cells based on conductive carbon black product 3 was 7.37 mΩ, while the average DC internal resistance of the cells based on raw carbon black 3 was 11.94 mΩ.

[0159] Example 4

[0160] This embodiment provides a conductive carbon black, the preparation method of which includes:

[0161] A 1L round-bottom flask equipped with a magnetic stirrer was transferred to an argon-atmosphere glove box and fixed on a heated magnetic stirring table. 456mL of dried toluene with a moisture content of 28ppm was added to the round-bottom flask. 100g of raw carbon black 4, dried at 85°C for 6 hours, was added to the round-bottom flask. The stirrer was started at 120rpm. The temperature was maintained within the range of 25±1°C. After five minutes, 2.352g of a mixture of mercuric iodide and mercuric oxide (1:1 molar ratio) was slowly added to the round-bottom flask using a spatula. In this embodiment, the ratio of the weight of raw carbon black 4 to the molar number of halogen atoms in the halogenating reagent was 1:0.1, and the raw carbon black accounted for 20% of the total mass of raw carbon black, halogenating reagent, and solvent. After the halogenating reagent was added, the temperature was raised to 100°C and stirring was continued for 18 hours. After the reaction was completed, the mixture was filtered using a vacuum filtration flask in a glove box. All the material in the round-bottom flask was slowly poured into a G4 sintered glass funnel lined with medium-speed filter paper. The filter residue was washed three times with 912 mL of toluene. The filter residue, along with the funnel, was transferred to a vacuum drying oven and dried at 80 °C for 18 h to obtain conductive carbon black precursor 4.

[0162] A 500 mL round-bottom flask equipped with a magnetic stirrer was transferred to an argon-atmosphere glove box and fixed on a heated magnetic stirring table. 146 mL of dried pyridine with a water content of 44 ppm was added to the round-bottom flask. 14.03 g of tert-butyldimethylsilylacetylene was added to the round-bottom flask. The stirrer was started at 120 rpm. The temperature was maintained at 25 ± 1 °C. After five minutes, 25.33 g of cuprous iodide was added to the round-bottom flask. In this example, the molar ratio of carbon black acetylation reagent to cuprous salt was 1:1.33, and the total concentration of carbon black acetylation reagent and cuprous salt in the solution was 1.6 mol / L. After the cuprous iodide was added, the temperature was raised to 80 °C and stirring was continued for 36 hours. After the reaction was completed, the mixture was filtered using a vacuum filtration flask in a glove box. All the material in the round-bottom flask was slowly poured into a G4 sintered glass funnel lined with medium-speed filter paper. The filter residue was washed three times with 438 mL of pyridine. The filter residue, along with the funnel, was transferred to a vacuum drying oven and dried at 80°C for 18 hours to obtain activated acetylation reagent 4.

[0163] Transfer a 1L round-bottom flask equipped with a magnetic stirrer to an argon-atmosphere glove box and secure it to a heated magnetic stirring table. Add 350mL of dried acetonitrile with a water content of 36ppm to the round-bottom flask. Add 70mL of dried triallylamine with a water content of 46ppm to the round-bottom flask. Add 0.396g of [1,2-bis(diphenylphosphine)ethane]palladium dichloride and 0.193g of tricyclohexylphosphine to the round-bottom flask. Start the stirrer at 240rpm. Maintain the temperature within the range of 25±1℃. After three minutes, add 100g of conductive carbon black precursor 4 to the round-bottom flask. Add 4.056g of activated acetylation reagent 4 to the round-bottom flask. In this embodiment, the volume ratio of the aprotic solvent to the organic tertiary amine is 1:0.2, the molar ratio of the catalyst to the co-catalyst is 1:1, the ratio of the kilogram of the conductive carbon black precursor to the molar amount of the activated acetylation reagent is 1:0.2, the total mass ratio of the catalyst and co-catalyst to the conductive carbon black precursor is 1:170, and the mass percentage of the conductive carbon black precursor in the total reaction system is 23%. After the activated acetylation reagent is added, the temperature is raised to 70°C and stirred continuously for 12 hours. After the reaction is completed, the mixture is filtered in a glove box using a vacuum filtration flask. All the material in the round-bottom flask is slowly poured into a G4 sintered glass funnel covered with medium-speed filter paper. The filter residue is washed twice with 840 mL of acetonitrile, and then washed three times with 630 mL of deionized water. The filter residue, along with the funnel, is transferred to a vacuum drying oven and dried at 70°C for 12 hours to obtain conductive carbon black sub-product 4.

[0164] A 1.5L round-bottom flask equipped with a magnetic stirrer was fixed on a magnetic stirring table with heating function. 550g of a 1.25mol / L potassium phosphate butanol solution was added to the round-bottom flask. The stirrer was started at 120rpm. The temperature was maintained within the range of 25±1℃. 100g of conductive carbon black sub-product 4 was added to the round-bottom flask. The temperature was raised to 70℃ and the stirring speed was maintained for 18 hours. After the reaction was completed, the mixture was filtered using a vacuum filtration flask. All the material in the round-bottom flask was slowly poured into a G4 sintered glass funnel covered with medium-speed filter paper. The filter residue was washed three times with 679mL of tetrahydrofuran, and then washed three times with 679mL of deionized water. The filter residue, along with the funnel, was transferred to a vacuum drying oven and dried at 70℃ for 12 hours to obtain conductive carbon black product 4.

[0165] This embodiment also provides a performance test experiment on the above-mentioned conductive carbon black finished product for soft-pack batteries. The test methods and results are as follows:

[0166] The conductive carbon black finished product 4 and the raw carbon black 4 were each used to assemble 15 cells according to the soft-pack battery formula 4 for performance testing. The results are shown in [link to results]. Figures 1 to 6 .

[0167] At 20℃, the average discharge capacity of the three 0.2C pouch cells based on conductive carbon black product 4 is 1.516Ah, and the average DC internal resistance is 1.97mΩ. The average discharge capacity of the three 0.2C pouch cells based on raw carbon black 4 is 1.509Ah, and the average DC internal resistance is 1.99mΩ. At -20℃, the average discharge capacity of the three 0.2C pouch cells based on conductive carbon black product 4 is 1.121Ah, and the average discharge capacity of the three 0.2C pouch cells based on raw carbon black 4 is 1.119Ah. At 20℃, the average discharge capacity of the three 1C pouch cells based on conductive carbon black product 4 is 1.426Ah, and the average discharge capacity of the three 1C pouch cells based on raw carbon black 4 is 1.427Ah.

[0168] At 20℃, after 1082, 1098, and 1094 charge-discharge cycles respectively, the discharge capacity retention rate of three pouch cells based on conductive carbon black product 4 decreased to 70%. After 825, 819, and 810 charge-discharge cycles respectively, the discharge capacity retention rate of three pouch cells based on raw carbon black 4 decreased to 70%. The average cycle life of the cells based on conductive carbon black product 4 increased by 33.41%. After 750 cycles, the average DC internal resistance of the cells based on conductive carbon black product 4 was 8.28 mΩ, while the average DC internal resistance of the cells based on raw carbon black 4 was 11.7 mΩ.

[0169] Example 5

[0170] This embodiment provides a conductive carbon black, the preparation method of which includes:

[0171] A 1L round-bottom flask equipped with a magnetic stirrer was transferred to an argon-atmosphere glove box and fixed on a heated magnetic stirring table. 554mL of dried diethyl ether with a moisture content of 31ppm was added to the round-bottom flask. 100g of raw carbon black 5, dried at 100°C for 12h, was added to the round-bottom flask. The stirrer was started at 120rpm. The temperature was maintained within the range of 25±1°C. After five minutes, 4.704g of a mixture of mercuric iodide and mercuric oxide (1:1 molar ratio) was slowly added to the round-bottom flask using a spatula. In this embodiment, the ratio of the weight of raw carbon black 5 to the molar number of halogen atoms in the halogenating reagent was 1:0.2, and the raw carbon black accounted for 20% of the total mass of raw carbon black, halogenating reagent, and solvent. After the halogenating reagent was added, the temperature and stirring speed were maintained, and stirring continued for 18h. After the reaction was completed, the mixture was filtered using a vacuum filtration flask in a glove box. All the material in the round-bottom flask was slowly poured into a G4 sintered glass funnel lined with medium-speed filter paper. The filter residue was washed three times with 1.384 L of diethyl ether. The filter residue, along with the funnel, was transferred to a vacuum drying oven and dried at 50 °C for 12 h to obtain conductive carbon black precursor 5.

[0172] A 500 mL round-bottom flask equipped with a magnetic stirrer was transferred to an argon-atmosphere glove box and fixed on a heated magnetic stirring table. 166 mL of dried dioxane with a water content of 40 ppm was added to the round-bottom flask. 14.03 g of triethylsilylacetylene was added to the round-bottom flask. The stirrer was started at 240 rpm. The temperature was maintained at 25 ± 1 °C. After five minutes, 25.33 g of cuprous iodide was added to the round-bottom flask. In this example, the molar ratio of carbon black acetylation reagent to cuprous salt was 1:1.33, and the total concentration of carbon black acetylation reagent and cuprous salt in the solution was 1.4 mol / L. After the cuprous iodide was added, the temperature was raised to 65 °C and stirring was continued for 36 hours. After the reaction was completed, the mixture was filtered using a vacuum filtration flask in a glove box. All the material in the round-bottom flask was slowly poured into a G4 sintered glass funnel lined with medium-speed filter paper. The filter residue was rinsed three times with 498 mL of dioxane. The filter residue, along with the funnel, was transferred to a vacuum drying oven and dried at 80°C for 18 hours to obtain the activated acetylation reagent 5.

[0173] Transfer a 1L round-bottom flask equipped with a magnetic stirrer to an argon-atmosphere glove box and secure it to a heated magnetic stirring table. Add 295mL of dried dioxane with a water content of 40ppm to the round-bottom flask. Add 30mL of dried tripropylamine with a water content of 37ppm to the round-bottom flask. Add 0.522g of bis(tricyclohexylphosphine)palladium dichloride and 0.478g of 2-tert-butylphosphine-1-benzylindole to the round-bottom flask. Start the stirrer at 360rpm. Maintain the temperature within the range of 25±1℃. After three minutes, add 100g of conductive carbon black precursor 5 to the round-bottom flask. Add 6.084g of activated acetylation reagent 5 to the round-bottom flask. In this embodiment, the volume ratio of the aprotic solvent to the organic tertiary amine is 1:0.1, the molar ratio of the catalyst to the co-catalyst is 1:2, the ratio of the kilogram of the conductive carbon black precursor to the molar number of the activated acetylation reagent is 1:0.3, the total mass ratio of the catalyst and co-catalyst to the conductive carbon black precursor is 1:100, and the mass percentage of the conductive carbon black precursor in the total reaction system is 23%. After the activated acetylation reagent is added, the temperature is raised to 90°C and stirred continuously for 6 hours. After the reaction is completed, the mixture is filtered in a glove box using a vacuum filtration flask. All the material in the round-bottom flask is slowly poured into a G4 sintered glass funnel covered with medium-speed filter paper. The filter residue is washed twice with 813 mL of dioxane, and then washed three times with 488 mL of deionized water. The filter residue, along with the funnel, is transferred to a vacuum drying oven and dried at 90°C for 18 hours to obtain conductive carbon black sub-product 5.

[0174] A 2L round-bottom flask equipped with a magnetic stirrer was fixed on a magnetic stirring table with heating function. 700g of a 1mol / L sodium bicarbonate isopropanol solution was added to the round-bottom flask. The stirrer was started at 180rpm. The temperature was maintained within the range of 25±1℃. 100g of conductive carbon black sub-product 5 was added to the round-bottom flask. The temperature was raised to 70℃ and the stirring speed was maintained for 18 hours. After the reaction was completed, the mixture was filtered using a vacuum filtration flask. All the material in the round-bottom flask was slowly poured into a G4 sintered glass funnel covered with medium-speed filter paper. The filter residue was washed three times with 1.338L of toluene, and then washed three times with 1.338L of deionized water. The filter residue, along with the funnel, was transferred to a vacuum drying oven and dried at 90℃ for 18 hours to obtain conductive carbon black product 5.

[0175] This embodiment also provides a performance test experiment on the above-mentioned conductive carbon black finished product for soft-pack batteries. The test methods and results are as follows:

[0176] Fifteen conductive carbon black products (finished product 5) and fifteen raw carbon black products (raw material 5) were assembled into 15 cells each according to the first formula for soft-pack batteries for performance testing. The results are shown below. Figures 1 to 6 .

[0177] At 20℃, the average discharge capacity of the three 0.2C pouch cells based on conductive carbon black product 5 is 1.494Ah, and the average DC internal resistance is 2.01mΩ. The average discharge capacity of the three 0.2C pouch cells based on raw carbon black 5 is 1.503Ah, and the average DC internal resistance is 2mΩ. At -20℃, the average discharge capacity of the three 0.2C pouch cells based on conductive carbon black product 5 is 1.112Ah, and the average discharge capacity of the three 0.2C pouch cells based on raw carbon black 5 is 1.118Ah. At 20℃, the average discharge capacity of the three 1C pouch cells based on conductive carbon black product 5 is 1.412Ah, and the average discharge capacity of the three 1C pouch cells based on raw carbon black 5 is 1.417Ah.

[0178] At 20℃, after 1136, 1127, and 1129 charge-discharge cycles respectively, the discharge capacity retention rate of three pouch cells based on conductive carbon black product 5 decreased to 70%. After 822, 818, and 825 charge-discharge cycles respectively, the discharge capacity retention rate of three pouch cells based on raw carbon black 5 decreased to 70%. The average cycle life of the cells based on conductive carbon black product 5 increased by 37.61%. After 750 cycles, the average DC internal resistance of the cells based on conductive carbon black product 5 was 8.09 mΩ, and the average DC internal resistance of the cells based on raw carbon black 5 was 12.42 mΩ.

[0179] Example 6

[0180] This embodiment provides a conductive carbon black, the preparation method of which includes:

[0181] A 1L round-bottom flask equipped with a magnetic stirrer was transferred to an argon-atmosphere glove box and fixed on a heated magnetic stirring table. 504 mL of dried tetrahydrofuran with a water content of 42 ppm was added to the round-bottom flask. 100 g of raw carbon black 6, dried at 100°C for 12 h, was added to the round-bottom flask. The stirrer was started at 120 rpm. The temperature was maintained within the range of 25 ± 1°C. After five minutes, 7.056 g of a mixture of mercuric iodide and mercuric oxide (1:1 molar ratio) was slowly added to the round-bottom flask using a spatula. In this embodiment, the ratio of the weight of raw carbon black 6 to the molar number of halogen atoms in the halogenating reagent was 1:0.3, and the raw carbon black accounted for 18% of the total mass of raw carbon black, halogenating reagent, and solvent. After the halogenating reagent was added, the temperature was raised to 45°C and stirring was continued for 18 h. After the reaction was completed, the mixture was filtered using a vacuum filtration flask in a glove box. All the material in the round-bottom flask was slowly poured into a G4 sintered glass funnel lined with medium-speed filter paper. The filter residue was washed three times with 1.5-12 L of tetrahydrofuran. The filter residue, along with the funnel, was transferred to a vacuum drying oven and dried at 50°C for 12 hours to obtain conductive carbon black precursor 6.

[0182] A 500 mL round-bottom flask equipped with a magnetic stirrer was transferred to an argon-atmosphere glove box and fixed on a heated magnetic stirring table. 192 mL of dried malononitrile with a water content of 35 ppm was added to the round-bottom flask. 14.03 g of triethylsilylacetylene was added to the round-bottom flask. The stirrer was started at 240 rpm. The temperature was maintained at 25 ± 1 °C. After five minutes, 24.759 g of cuprous iodide was added to the round-bottom flask. In this example, the molar ratio of carbon black acetylation reagent to cuprous salt was 1:1.3, and the total concentration of carbon black acetylation reagent and cuprous salt in the solution was 1.2 mol / L. After the cuprous iodide was added, the temperature was raised to 65 °C and stirring was continued for 48 hours. After the reaction was completed, the mixture was filtered using a vacuum filtration flask in a glove box. All the material in the round-bottom flask was slowly poured into a G4 sintered glass funnel lined with medium-speed filter paper. The filter residue was washed three times with 480 mL of malononitrile. The filter residue, along with the funnel, was transferred to a vacuum drying oven and dried at 80°C for 18 hours to obtain activated acetylation reagent 6.

[0183] Transfer a 1L round-bottom flask equipped with a magnetic stirrer to an argon-atmosphere glove box and secure it to a heated magnetic stirring table. Add 329mL of dried dioxane with a water content of 40ppm to the round-bottom flask. Add 82mL of dried dicyclohexylmethylamine with a water content of 34ppm to the round-bottom flask. Add 0.369g of bis(acetonitrile)palladium dichloride and 0.881g of 1,3-bis(diphenylphosphine)propane to the round-bottom flask. Start the stirrer at 360rpm. Maintain the temperature within the range of 25±1℃. After three minutes, add 100g of conductive carbon black precursor 6 to the round-bottom flask. Add 10.14g of activated acetylation reagent 6 to the round-bottom flask. In this embodiment, the volume ratio of the aprotic solvent to the organic tertiary amine is 1:0.25, the molar ratio of the catalyst to the co-catalyst is 1:1.5, the ratio of the kilogram of the conductive carbon black precursor to the molar number of the activated acetylation reagent is 1:0.5, the total mass ratio of the catalyst and co-catalyst to the conductive carbon black precursor is 1:80, and the mass percentage of the conductive carbon black precursor in the total reaction system is 19%. After the activated acetylation reagent is added, the temperature is raised to 90°C and stirred continuously for 12 hours. After the reaction is completed, the mixture is filtered in a glove box using a vacuum filtration flask. All the material in the round-bottom flask is slowly poured into a G4 sintered glass funnel covered with medium-speed filter paper. The filter residue is washed twice with 1.028 L of dioxane, and then washed three times with 617 mL of deionized water. The filter residue, along with the funnel, is transferred to a vacuum drying oven and dried at 90°C for 18 hours to obtain conductive carbon black sub-product 6.

[0184] A 2L round-bottom flask equipped with a magnetic stirrer was fixed on a magnetic stirring table with heating function. 700g of a 1mol / L potassium bicarbonate solution in propanol was added to the round-bottom flask. The stirrer was started at 180rpm. The temperature was maintained within the range of 25±1℃. 100g of conductive carbon black sub-product 6 was added to the round-bottom flask. The temperature and stirring speed were maintained, and stirring continued for 48h. After the reaction was completed, the mixture was filtered using a vacuum filtration flask. All the material in the round-bottom flask was slowly poured into a G4 sintered glass funnel covered with medium-speed filter paper. The filter residue was washed three times with 1.307L of toluene, and then three times with 1.307L of deionized water. The filter residue, along with the funnel, was transferred to a vacuum drying oven and dried at 90℃ for 18h to obtain conductive carbon black product 6.

[0185] This embodiment also provides a performance test experiment on the above-mentioned conductive carbon black finished product for soft-pack batteries. The test methods and results are as follows:

[0186] Fifteen conductive carbon black finished product 6 and 15 raw carbon black 6 were assembled into cells according to the second formula for soft-pack batteries, respectively, for performance testing. The results are shown below. Figures 1 to 6 .

[0187] At 20℃, the average discharge capacity of the three 0.2C pouch cells based on conductive carbon black product 6 is 1.51Ah, and the average DC internal resistance is 1.97mΩ. The average discharge capacity of the three 0.2C pouch cells based on raw carbon black 6 is 1.497Ah, and the average DC internal resistance is 2mΩ. At -20℃, the average discharge capacity of the three 0.2C pouch cells based on conductive carbon black product 6 is 1.113Ah, and the average discharge capacity of the three 0.2C pouch cells based on raw carbon black 6 is 1.117Ah. At 20℃, the average discharge capacity of the three 1C pouch cells based on conductive carbon black product 6 is 1.412Ah, and the average discharge capacity of the three 1C pouch cells based on raw carbon black 6 is 1.401Ah.

[0188] At 20℃, after 1144, 1152, and 1163 charge-discharge cycles respectively, the discharge capacity retention rate of three pouch cells based on conductive carbon black product 6 decreased to 70%. After 815, 822, and 818 charge-discharge cycles respectively, the discharge capacity retention rate of three pouch cells based on raw carbon black 6 decreased to 70%. The average cycle life of the cells based on conductive carbon black product 6 increased by 40.9%. After 750 cycles, the average DC internal resistance of the cells based on conductive carbon black product 6 was 7.9 mΩ, while the average DC internal resistance of the cells based on raw carbon black 6 was 11.46 mΩ.

[0189] Example 7

[0190] This embodiment provides a conductive carbon black, the preparation method of which includes:

[0191] A 1L round-bottom flask equipped with a magnetic stirrer was transferred to an argon-atmosphere glove box and fixed on a heated magnetic stirring table. 454mL of dried pyridine with a moisture content of 44ppm was added to the round-bottom flask. 100g of raw carbon black 7, dried at 115°C for 12h, was added to the round-bottom flask. The stirrer was started at 240rpm. The temperature was maintained within the range of 25±1°C. After five minutes, 8.999g of N-iodosuccinimide was slowly added to the round-bottom flask using a spatula. In this example, the ratio of the weight of raw carbon black 7 to the molar number of halogen atoms in N-iodosuccinimide was 1:0.4, and the percentage of raw carbon black in the total mass of raw carbon black, halogenating reagent, and solvent was 18%. After the halogenating reagent was added, the temperature was raised to 90°C and stirring was continued for 24h. After the reaction was completed, the mixture was filtered using a vacuum filtration flask in a glove box. All the material in the round-bottom flask was slowly poured into a G4 sintered glass funnel lined with medium-speed filter paper. The filter residue was washed three times with 909 mL of pyridine. The filter residue, along with the funnel, was transferred to a vacuum drying oven and dried at 110 °C for 18 h to obtain conductive carbon black precursor 7.

[0192] An 8L round-bottom flask equipped with a magnetic stirrer was transferred to an argon-atmosphere glove box and fixed on a heated magnetic stirring table. 4.101L of dried methyl ethyl ketone (MEK) with a water content of 33ppm was added to the round-bottom flask. 29.466g of trimethylsilylacetylene was added to the round-bottom flask. The stirrer was started at 360rpm. The temperature was maintained at 25±1℃. After five minutes, 50.136g of cuprous sulfide was added to the round-bottom flask. In this example, the molar ratio of carbon black acetylation reagent to cuprous salt was 1:1.05, and the total concentration of carbon black acetylation reagent and cuprous salt in the solution was 0.15mol / L. After the cuprous sulfide was added, the temperature was raised to 45℃ and stirring was continued for 48 hours. After the reaction was completed, the mixture was filtered using a vacuum filtration flask in a glove box. All the material in the round-bottom flask was slowly poured into a G4 sintered glass funnel lined with medium-speed filter paper. The filter residue was washed three times with 10.254 L of butanone. The filter residue, along with the funnel, was transferred to a vacuum drying oven and dried at 70°C for 18 hours to obtain the activated acetylation reagent 7.

[0193] Transfer a 1L round-bottom flask equipped with a magnetic stirrer to an argon-atmosphere glove box and secure it to a heated magnetic stirring table. Add 340mL of dried N,N-dimethylformamide with a water content of 35ppm to the round-bottom flask. Add 102mL of dried 1,4-diethylpiperazine with a water content of 41ppm to the round-bottom flask. Add 0.587g of bis(diphenylacetone)palladium and 0.842g of 1,3-bis(diphenylphosphine)propane to the round-bottom flask. Start the stirrer at 480rpm. Maintain the temperature within the range of 25±1℃. After three minutes, add 100g of conductive carbon black precursor 7 to the round-bottom flask. Add 11.25g of activated acetylation reagent 7 to the round-bottom flask. In this embodiment, the volume ratio of the aprotic solvent to the organic tertiary amine is 1:0.3, the molar ratio of the catalyst to the co-catalyst is 1:2, the ratio of the kilogram of the conductive carbon black precursor to the molar amount of the activated acetylation reagent is 1:0.7, the total mass ratio of the catalyst and co-catalyst to the conductive carbon black precursor is 1:70, and the mass percentage of the conductive carbon black precursor in the total reaction system is 19%. After the activated acetylation reagent is added, the temperature is raised to 110°C and stirred continuously for 18 hours. After the reaction is completed, the mixture is filtered in a glove box using a vacuum filtration flask. All the material in the round-bottom flask is slowly poured into a G4 sintered glass funnel covered with medium-speed filter paper. The filter residue is washed twice with 1.326 L N,N-dimethylformamide, and then washed three times with 884 mL deionized water. The filter residue, along with the funnel, is transferred to a vacuum drying oven and dried at 100°C for 18 hours to obtain conductive carbon black sub-product 7.

[0194] A 2L round-bottom flask equipped with a magnetic stirrer was fixed on a magnetic stirring table with heating function. 700g of a 1mol / L sodium sulfide ethanol solution was added to the round-bottom flask. The stirrer was started at 180rpm. The temperature was maintained within the range of 25±1℃. 100g of conductive carbon black sub-product 1 was added to the round-bottom flask. The temperature and stirring speed were maintained, and stirring continued for 48h. After the reaction was completed, the mixture was filtered using a vacuum filtration flask. All the material in the round-bottom flask was slowly poured into a G4 sintered glass funnel covered with medium-speed filter paper. The filter residue was washed three times with 1.331L of toluene, and then three times with 1.331L of deionized water. The filter residue, along with the funnel, was transferred to a vacuum drying oven and dried at 90℃ for 18h to obtain conductive carbon black product 7.

[0195] This embodiment also provides a performance test experiment on the above-mentioned conductive carbon black finished product for soft-pack batteries. The test methods and results are as follows:

[0196] Fifteen conductive carbon black finished product 7 and 15 raw carbon black 7 were assembled into cells according to the soft-pack battery formula 3 for performance testing. The results are shown below. Figures 1 to 6 .

[0197] At 20℃, the average discharge capacity of the three 0.2C pouch cells based on conductive carbon black product 7 is 1.516Ah, and the average DC internal resistance is 1.98mΩ. The average discharge capacity of the three 0.2C pouch cells based on raw carbon black 7 is 1.508Ah, and the average DC internal resistance is 1.99mΩ. At -20℃, the average discharge capacity of the three 0.2C pouch cells based on conductive carbon black product 7 is 1.117Ah, and the average discharge capacity of the three 0.2C pouch cells based on raw carbon black 7 is 1.112Ah. At 20℃, the average discharge capacity of the three 1C pouch cells based on conductive carbon black product 7 is 1.418Ah, and the average discharge capacity of the three 1C pouch cells based on raw carbon black 7 is 1.409Ah.

[0198] At 20℃, after 1246, 1229, and 1235 charge-discharge cycles respectively, the discharge capacity retention rate of three pouch cells based on conductive carbon black product 7 decreased to 70%. After 869, 884, and 871 charge-discharge cycles respectively, the discharge capacity retention rate of three pouch cells based on raw carbon black 7 decreased to 70%. The average cycle life of the cells based on conductive carbon black product 7 increased by 41.39%. After 750 cycles, the average DC internal resistance of the cells based on conductive carbon black product 7 was 6.04 mΩ, while the average DC internal resistance of the cells based on raw carbon black 7 was 10.38 mΩ.

[0199] Example 8

[0200] This embodiment provides a conductive carbon black, the preparation method of which includes:

[0201] A 1L round-bottom flask equipped with a magnetic stirrer was transferred to an argon-atmosphere glove box and fixed on a heated magnetic stirring table. 467mL of dried N,N-dimethylformamide with a water content of 35ppm was added to the round-bottom flask. 100g of raw carbon black 8, dried at 115°C for 12h, was added to the round-bottom flask. The stirrer was started at 240rpm. The temperature was maintained within the range of 25±1°C. After five minutes, 12.374g of N-iodosuccinimide was slowly added to the round-bottom flask using a spatula. In this embodiment, the ratio of the weight of raw carbon black 8 to the molar number of halogen atoms in iodine chloride was 1:0.55, and the percentage of raw carbon black in the total mass of raw carbon black, halogenating reagent, and solvent was 18%. After the halogenating reagent was added, the temperature was raised to 112°C and stirring was continued for 24h. After the reaction was completed, the mixture was filtered using a vacuum filtration flask in a glove box. All the material in the round-bottom flask was slowly poured into a G4 sintered glass funnel lined with medium-speed filter paper. The filter residue was washed three times with 1.402 L of N,N-dimethylformamide. The filter residue, along with the funnel, was transferred to a vacuum drying oven and dried at 130°C for 24 hours to obtain conductive carbon black precursor 8.

[0202] An 8L round-bottom flask equipped with a magnetic stirrer was transferred to an argon-atmosphere glove box and fixed on a heated magnetic stirring table. 4.2L of dried acetonitrile with a moisture content of 36ppm was added to the round-bottom flask. 29.466g of trimethylsilylacetylene was added to the round-bottom flask. The stirrer was started at 360rpm. The temperature was maintained at 25±1℃. After five minutes, 47.22g of cuprous oxide was added to the round-bottom flask. In this example, the molar ratio of carbon black acetylation reagent to cuprous salt was 1:1.1, and the total concentration of carbon black acetylation reagent and cuprous salt in the solution was 0.15mol / L. After the cuprous iodide was added, the temperature was raised to 45℃ and stirring was continued for 48 hours. After the reaction was completed, the mixture was filtered using a vacuum filtration flask in a glove box. All the material in the round-bottom flask was slowly poured into a G4 sintered glass funnel lined with medium-speed filter paper. The filter residue was washed three times with 10.5 L of acetonitrile. The filter residue, along with the funnel, was transferred to a vacuum drying oven and dried at 70°C for 18 hours to obtain the activated acetylation reagent 8.

[0203] Transfer a 1L round-bottom flask equipped with a magnetic stirrer to an argon-atmosphere glove box and secure it to a heated magnetic stirring table. Add 356mL of dried N,N-dimethylformamide with a water content of 35ppm to the round-bottom flask. Add 89mL of dried 1-ethylpyrrolidine with a water content of 46ppm to the round-bottom flask. Add 0.235g of 1,5-cyclooctadiene palladium dichloride and 0.876g of 1,4-bis(diphenylphosphine)butane to the round-bottom flask. Start the stirrer at 480rpm. Maintain the temperature within the range of 25±1℃. After three minutes, add 100g of conductive carbon black precursor 8 to the round-bottom flask. Add 16.072g of activated acetylation reagent 8 to the round-bottom flask. In this embodiment, the volume ratio of the aprotic solvent to the organic tertiary amine is 1:0.25, the molar ratio of the catalyst to the co-catalyst is 1:2.5, the ratio of the kilogram of the conductive carbon black precursor to the molar amount of the activated acetylation reagent is 1:1, the total mass ratio of the catalyst and co-catalyst to the conductive carbon black precursor is 1:90, and the mass percentage of the conductive carbon black precursor in the total reaction system is 19%. After the activated acetylation reagent is added, the temperature is raised to 110°C and stirred continuously for 18 hours. After the reaction is completed, the mixture is filtered in a glove box using a vacuum filtration flask. All the material in the round-bottom flask is slowly poured into a G4 sintered glass funnel covered with medium-speed filter paper. The filter residue is washed twice with 1.335 L of N,N-dimethylformamide, and then washed three times with 890 mL of deionized water. The filter residue, along with the funnel, is transferred to a vacuum drying oven and dried at 100°C for 18 hours to obtain conductive carbon black sub-product 8.

[0204] A 2L round-bottom flask equipped with a magnetic stirrer was fixed on a magnetic stirring table with heating function. 1000g of a 0.8mol / L sodium thiosulfate solution in ethylenediamine was added to the round-bottom flask. The stirrer was started at 240rpm. The temperature was maintained within the range of 25±1℃. 100g of conductive carbon black sub-product 8 was added to the round-bottom flask. The temperature was raised to 85℃ and the stirring speed was maintained for 24 hours. After the reaction was completed, the mixture was filtered using a vacuum filtration flask. All the material in the round-bottom flask was slowly poured into a G4 sintered glass funnel covered with medium-speed filter paper. The filter residue was washed three times with 1.668L of dichloromethane, and then three times with 1.668L of deionized water. The filter residue, along with the funnel, was transferred to a vacuum drying oven and dried at 90℃ for 18 hours to obtain conductive carbon black product 8.

[0205] This embodiment also provides a performance test experiment on the above-mentioned conductive carbon black finished product for soft-pack batteries. The test methods and results are as follows:

[0206] The conductive carbon black finished product 8 and the raw carbon black 8 were respectively assembled into 15 cells according to the soft-pack battery formula 4 for performance testing. The results are shown in [link to results]. Figures 1 to 6.

[0207] At 20℃, the average discharge capacity of the three 0.2C pouch cells based on conductive carbon black product 8 is 1.512Ah, and the average DC internal resistance is 2.03mΩ. The average discharge capacity of the three 0.2C pouch cells based on raw carbon black 8 is 1.52Ah, and the average DC internal resistance is 1.99mΩ. At -20℃, the average discharge capacity of the three 0.2C pouch cells based on conductive carbon black product 8 is 1.122Ah, and the average discharge capacity of the three 0.2C pouch cells based on raw carbon black 8 is 1.114Ah. At 20℃, the average discharge capacity of the three 1C pouch cells based on conductive carbon black product 8 is 1.414Ah, and the average discharge capacity of the three 1C pouch cells based on raw carbon black 8 is 1.418Ah.

[0208] At 20℃, after 1332, 1309, and 1324 charge-discharge cycles respectively, the discharge capacity retention rate of three pouch cells based on conductive carbon black product 8 decreased to 70%. After 927, 921, and 936 charge-discharge cycles respectively, the discharge capacity retention rate of three pouch cells based on raw carbon black 8 decreased to 70%. The average cycle life of the cells based on conductive carbon black product 8 increased by 42.42%. After 750 cycles, the average DC internal resistance of the cells based on conductive carbon black product 8 was 5.58 mΩ, and the average DC internal resistance of the cells based on raw carbon black 8 was 9.44 mΩ.

[0209] Example 9

[0210] This embodiment provides a conductive carbon black, the preparation method of which includes:

[0211] A 1L round-bottom flask equipped with a magnetic stirrer was transferred to an argon-atmosphere glove box and fixed on a heated magnetic stirring table. 501mL of dried dimethyl sulfoxide (DMSO) with a moisture content of 37ppm was added to the round-bottom flask. 100g of raw carbon black 9, dried at 130°C for 18h, was added to the round-bottom flask. The stirrer was started at 240rpm. The temperature was maintained within the range of 25±1°C. After five minutes, 15.074g of N-iodosuccinimide was slowly added to the round-bottom flask using a spatula. In this embodiment, the ratio of the weight of raw carbon black 9 to the molar number of halogen atoms in N-iodosuccinimide was 1:0.67, and the raw carbon black accounted for 15% of the total mass of raw carbon black, halogenating reagent, and solvent. After the halogenating reagent was added, the temperature was raised to 125°C and stirring was continued for 24h. After the reaction was completed, the mixture was filtered using a vacuum filtration flask in a glove box. All the material in the round-bottom flask was slowly poured into a G4 sintered glass funnel lined with medium-speed filter paper. The filter residue was washed three times with 1.504 L of dimethyl sulfoxide. The filter residue, along with the funnel, was transferred to a vacuum drying oven and dried at 130°C for 24 hours to obtain conductive carbon black precursor 9.

[0212] A 2L round-bottom flask equipped with a magnetic stirrer was transferred to an argon-atmospheric glove box and fixed on a heated magnetic stirring table. 1.125L of dried isopropyl ether with a water content of 26ppm was added to the round-bottom flask. 29.466g of trimethylsilylacetylene was added to the round-bottom flask. The stirrer was started at 480rpm. The temperature was maintained at 25±1℃. After five minutes, 45.612g of cuprous thiocyanate was added to the round-bottom flask. In this example, the molar ratio of carbon black acetylation reagent to cuprous salt was 1:1.25, and the total concentration of carbon black acetylation reagent and cuprous salt in the solution was 0.6mol / L. After the cuprous thiocyanate was added, the temperature was raised to 35℃ and stirring was continued for 48 hours. After the reaction was completed, the mixture was filtered using a vacuum filtration flask in a glove box. All the material in the round-bottom flask was slowly poured into a G4 sintered glass funnel lined with medium-speed filter paper. The filter residue was washed three times with 2.25 L of isopropyl ether. The filter residue, along with the funnel, was transferred to a vacuum drying oven and dried at 50°C for 12 hours to obtain the activated acetylation reagent 9.

[0213] Transfer a 1.5L round-bottom flask equipped with a magnetic stirrer to an argon-atmosphere glove box and secure it to a heated magnetic stirring table. Add 725mL of dried N,N-dimethylformamide with a water content of 35ppm to the round-bottom flask. Add 239mL of dried 1-butylpyrrolidine with a water content of 40ppm to the round-bottom flask. Add 0.541g of palladium hexafluoroacetylacetone and 0.887g of 1,4-bis(diphenylphosphine)butane to the round-bottom flask. Start the stirrer at 480rpm. Maintain the temperature within the range of 25±1℃. After three minutes, add 100g of conductive carbon black precursor 9 to the round-bottom flask. Add 16.072g of activated acetylation reagent 9 to the round-bottom flask. In this embodiment, the volume ratio of the aprotic solvent to the organic tertiary amine is 1:0.33, the molar ratio of the catalyst to the co-catalyst is 1:2, the ratio of the kilogram of the conductive carbon black precursor to the molar amount of the activated acetylation reagent is 1:1, the total mass ratio of the catalyst and co-catalyst to the conductive carbon black precursor is 1:70, and the mass percentage of the conductive carbon black precursor in the total reaction system is 10%. After the activated acetylation reagent is added, the temperature is raised to 110°C and stirred continuously for 18 hours. After the reaction is completed, the mixture is filtered in a glove box using a vacuum filtration flask. All the material in the round-bottom flask is slowly poured into a G4 sintered glass funnel covered with medium-speed filter paper. The filter residue is washed twice with 2.892 L of N,N-dimethylformamide, and then washed three times with 1.928 L of deionized water. The filter residue, along with the funnel, is transferred to a vacuum drying oven and dried at 130°C for 24 hours to obtain conductive carbon black sub-product 9.

[0214] A 3L round-bottom flask equipped with a magnetic stirrer was fixed on a magnetic stirring table with heating function. 1000g of a 0.8mol / L sodium acetate solution in propylamine was added to the round-bottom flask. The stirrer was started at 240rpm. The temperature was maintained within the range of 25±1℃. 100g of conductive carbon black sub-finished product 9 was added to the round-bottom flask. The temperature and stirring speed were maintained, and stirring continued for 48h. After the reaction was completed, the mixture was filtered using a vacuum filtration flask. All the material in the round-bottom flask was slowly poured into a G4 sintered glass funnel covered with medium-speed filter paper. The filter residue was washed three times with 2.778L of dichloromethane, and then three times with 2.778L of deionized water. The filter residue, along with the funnel, was transferred to a vacuum drying oven and dried at 90℃ for 24h to obtain conductive carbon black product 9.

[0215] This embodiment also provides a performance test experiment on the above-mentioned conductive carbon black finished product for soft-pack batteries. The test methods and results are as follows:

[0216] Fifteen conductive carbon black finished product 9 and 15 raw carbon black 9 were assembled into cells according to the soft-pack battery formula 5 for performance testing. The results are shown below. Figures 1 to 6 .

[0217] At 20℃, the average discharge capacity of the three 0.2C pouch cells based on conductive carbon black product 9 is 1.505Ah, and the average DC internal resistance is 4.13mΩ. The average discharge capacity of the three 0.2C pouch cells based on raw carbon black 9 is 1.513Ah, and the average DC internal resistance is 4.2mΩ. At -20℃, the average discharge capacity of the three 0.2C pouch cells based on conductive carbon black product 9 is 1.102Ah, and the average discharge capacity of the three 0.2C pouch cells based on raw carbon black 9 is 1.11Ah. At 20℃, the average discharge capacity of the three 1C pouch cells based on conductive carbon black product 9 is 1.408Ah, and the average discharge capacity of the three 1C pouch cells based on raw carbon black 9 is 1.411Ah.

[0218] At 20℃, after 1294, 1321, and 1285 charge-discharge cycles respectively, the discharge capacity retention rate of three pouch cells based on conductive carbon black product 9 decreased to 70%. After 893, 889, and 908 charge-discharge cycles respectively, the discharge capacity retention rate of three pouch cells based on raw carbon black 9 decreased to 70%. The average cycle life of the cells based on conductive carbon black product 9 increased by 44.98%. After 750 cycles, the average DC internal resistance of the cells based on conductive carbon black product 9 was 9.81 mΩ, while the average DC internal resistance of the cells based on raw carbon black 9 was 17.1 mΩ.

[0219] Example 10

[0220] This embodiment provides a conductive carbon black, the preparation method of which includes:

[0221] A 1.5L round-bottom flask equipped with a magnetic stirrer was transferred to an argon-atmosphere glove box and fixed on a heated magnetic stirring table. 714mL of dried acetone with a water content of 36ppm was added to the round-bottom flask. 100g of raw carbon black 10, dried at 130℃ for 18h, was added to the round-bottom flask. The stirrer was started at 120rpm. The temperature was maintained within the range of 25±1℃. After five minutes, 1.598g of liquid bromine was added dropwise to the round-bottom flask using a syringe. In this embodiment, the ratio of the kilograms of raw carbon black 10 to the molars of halogen atoms in the liquid bromine was 1:0.2, and the percentage of raw carbon black in the total mass of raw carbon black, halogenating reagent, and solvent was 15%. After the halogenating reagent was added, stirring was continued for 12h while maintaining the temperature and stirring speed. After the reaction was completed, the mixture was filtered using a vacuum filtration flask in a glove box. All the material in the round-bottom flask was slowly poured into a G4 sintered glass funnel lined with medium-speed filter paper. The filter residue was washed three times with 1.583 L of acetone. The filter residue, along with the funnel, was transferred to a vacuum drying oven and dried at 50 °C for 12 h to obtain conductive carbon black precursor 10.

[0222] A 3L round-bottom flask equipped with a magnetic stirrer was transferred to an argon-atmosphere glove box and fixed on a heated magnetic stirring table. 1.5L of dried petroleum ether with a water content of 24ppm was added to the round-bottom flask. 29.466g of trimethylsilylacetylene was added to the round-bottom flask. The stirrer was started at 480rpm. The temperature was maintained at 25±1℃. After five minutes, 33.585g of cuprous cyanide was added to the round-bottom flask. In this example, the molar ratio of carbon black acetylation reagent to cuprous salt was 1:1.25, and the total concentration of carbon black acetylation reagent and cuprous salt in the solution was 0.45mol / L. After the cuprous cyanide was added, the temperature was raised to 35℃ and stirring was continued for 48 hours. After the reaction was completed, the mixture was filtered using a vacuum filtration flask in a glove box. All the material in the round-bottom flask was slowly poured into a G4 sintered glass funnel lined with medium-speed filter paper. The filter residue was washed three times with 3L of petroleum ether. The filter residue, along with the funnel, was transferred to a vacuum drying oven and dried at 50°C for 12 hours to obtain activated acetylation reagent 10.

[0223] Transfer a 1.5L round-bottom flask equipped with a magnetic stirrer to an argon-atmosphere glove box and secure it to a heated magnetic stirring table. Add 659mL of dried dimethyl sulfoxide (DMSO) with a water content of 37ppm to the round-bottom flask. Add 198mL of dried tripentylamine (TMA) with a water content of 37ppm to the round-bottom flask. Add 0.376g of palladium dichloride (di(cyanobenzene)) and 1.053g of n-butyldi(1-adamantyl)phosphine to the round-bottom flask. Start the stirrer at 600rpm. Maintain the temperature within the range of 25±1℃. After three minutes, add 100g of conductive carbon black precursor 10 to the round-bottom flask. Add 19.286g of activated acetylation reagent 10 to the round-bottom flask. In this embodiment, the volume ratio of the aprotic solvent to the organic tertiary amine is 1:0.3, the molar ratio of the catalyst to the co-catalyst is 1:3, the ratio of the kilogram of the conductive carbon black precursor to the molar amount of the activated acetylation reagent is 1:1.2, the total mass ratio of the catalyst and co-catalyst to the conductive carbon black precursor is 1:70, and the mass percentage of the conductive carbon black precursor in the total reaction system is 10%. After the activated acetylation reagent is added, the temperature is raised to 150°C and stirred continuously for 24 hours. After the reaction is completed, the mixture is filtered in a glove box using a vacuum filtration flask. All the material in the round-bottom flask is slowly poured into a G4 sintered glass funnel covered with medium-speed filter paper. The filter residue is washed twice with 2.571 L of dimethyl sulfoxide, and then washed three times with 1.714 L of deionized water. The filter residue, along with the funnel, is transferred to a vacuum drying oven and dried at 130°C for 24 hours to obtain conductive carbon black sub-product 10.

[0224] A 3L round-bottom flask equipped with a magnetic stirrer was fixed on a magnetic stirring table with heating function. 1000g of a 0.8mol / L diethylamine solution of potassium acetate was added to the round-bottom flask. The stirrer was started at 240rpm. The temperature was maintained within the range of 25±1℃. 100g of conductive carbon black sub-product 10 was added to the round-bottom flask. The temperature was raised to 50℃ and the stirring speed was maintained, and stirring was continued for 24h. After the reaction was completed, the mixture was filtered using a vacuum filtration flask. All the material in the round-bottom flask was slowly poured into a G4 sintered glass funnel covered with medium-speed filter paper. The filter residue was washed three times with 2.816L of dichloromethane, and then three times with 2.816L of deionized water. The filter residue, along with the funnel, was transferred to a vacuum drying oven and dried at 90℃ for 24h to obtain conductive carbon black product 10.

[0225] This embodiment also provides a performance test experiment on the above-mentioned conductive carbon black finished product for soft-pack batteries. The test methods and results are as follows:

[0226] The conductive carbon black finished product 10 and the raw carbon black 10 were respectively assembled into 15 cells according to the soft-pack battery formula six for performance testing. The results are shown in [link to results]. Figures 1 to 6 .

[0227] At 20℃, the average discharge capacity of the three 0.2C pouch cells based on conductive carbon black product 10 is 1.511Ah, and the average DC internal resistance is 4.15mΩ. The average discharge capacity of the three 0.2C pouch cells based on raw carbon black product 10 is 1.499Ah, and the average DC internal resistance is 4.25mΩ. At -20℃, the average discharge capacity of the three 0.2C pouch cells based on conductive carbon black product 10 is 1.103Ah, and the average discharge capacity of the three 0.2C pouch cells based on raw carbon black product 10 is 1.096Ah. At 20℃, the average discharge capacity of the three 1C pouch cells based on conductive carbon black product 10 is 1.392Ah, and the average discharge capacity of the three 1C pouch cells based on raw carbon black product 10 is 1.399Ah.

[0228] At 20℃, after 1146, 1161, and 1155 charge-discharge cycles respectively, the discharge capacity retention rate of three pouch cells based on conductive carbon black product 10 decreased to 70%. After 858, 851, and 864 charge-discharge cycles respectively, the discharge capacity retention rate of three pouch cells based on raw carbon black 10 decreased to 70%. The average cycle life of the cells based on conductive carbon black product 10 increased by 34.55%. After 750 cycles, the average DC internal resistance of the cells based on conductive carbon black product 10 was 15.33 mΩ, and the average DC internal resistance of the cells based on raw carbon black 10 was 19.4 mΩ.

[0229] Example 11

[0230] This embodiment provides a conductive carbon black, the preparation method of which includes:

[0231] A 1.5L round-bottom flask equipped with a magnetic stirrer was transferred to an argon-atmosphere glove box and fixed on a heated magnetic stirring table. 714mL of dried acetone with a water content of 36ppm was added to the round-bottom flask. 100g of raw carbon black 1, dried at 145℃ for 18h, was added to the round-bottom flask. The stirrer was started at 720rpm. The temperature was maintained within the range of 25±1℃. After five minutes, 2.397g of liquid bromine was added dropwise to the round-bottom flask using a syringe. In this embodiment, the ratio of the weight of raw carbon black 11 to the molar number of halogen atoms in the liquid bromine was 1:0.3, and the raw carbon black accounted for 15% of the total mass of raw carbon black, halogenating reagent, and solvent. After the halogenating reagent was added, the temperature and stirring speed were maintained, and stirring continued for 12h. After the reaction was completed, the mixture was filtered using a vacuum filtration flask in a glove box. All the material in the round-bottom flask was slowly poured into a G4 sintered glass funnel lined with medium-speed filter paper. The filter residue was washed three times with 1.429 L of acetone. The filter residue, along with the funnel, was transferred to a vacuum drying oven and dried at 50 °C for 12 h to obtain conductive carbon black precursor 11.

[0232] A 5L round-bottom flask equipped with a magnetic stirrer was transferred to an argon-atmosphere glove box and fixed on a heated magnetic stirring table. 2.25L of dried diethyl ether with a water content of 31ppm was added to the round-bottom flask. 29.466g of trimethylsilylacetylene was added to the round-bottom flask. The stirrer was started at 600rpm. The temperature was maintained at 25±1℃. After five minutes, 45.972g of cuprous acetate was added to the round-bottom flask. In this example, the molar ratio of carbon black acetylation reagent to cuprous salt was 1:1.25, and the total concentration of carbon black acetylation reagent and cuprous salt in the solution was 0.3mol / L. After the cuprous acetate was added, the temperature and stirring speed were maintained for 48 hours. After the reaction was completed, the mixture was filtered using a vacuum filtration flask in a glove box. All the material in the round-bottom flask was slowly poured into a G4 sintered glass funnel lined with medium-speed filter paper. The filter residue was washed three times with 4.5 L of diethyl ether. The filter residue, along with the funnel, was transferred to a vacuum drying oven and dried at 50 °C for 12 h to obtain activated acetylation reagent 11.

[0233] Transfer a 1.5L round-bottom flask equipped with a magnetic stirrer to an argon-atmosphere glove box and secure it to a heated magnetic stirring table. Add 641mL of dried dimethyl sulfoxide (DMSO) with a water content of 37ppm to the round-bottom flask. Add 211mL of dried N-ethylpiperidine (N-ethylpiperidine) with a water content of 43ppm to the round-bottom flask. Add 0.82g of dichlorobis(tri-O-toluidine)palladium and 0.847g of tris(2-furanyl)phosphine to the round-bottom flask. Start the stirrer at 600rpm. Maintain the temperature within the range of 25±1℃. After three minutes, add 100g of conductive carbon black precursor 11 to the round-bottom flask. Add 19.286g of activated acetylation reagent 11 to the round-bottom flask. In this embodiment, the volume ratio of the aprotic solvent to the organic tertiary amine is 1:0.33, the molar ratio of the catalyst to the co-catalyst is 1:3.5, the ratio of the kilogram of the conductive carbon black precursor to the molar number of the activated acetylation reagent is 1:1.2, the total mass ratio of the catalyst and co-catalyst to the conductive carbon black precursor is 1:60, and the mass percentage of the conductive carbon black precursor in the total reaction system is 10%. After the activated acetylation reagent is added, the temperature is raised to 150°C and stirred continuously for 24 hours. After the reaction is completed, the mixture is filtered in a glove box using a vacuum filtration flask. All the material in the round-bottom flask is slowly poured into a G4 sintered glass funnel covered with medium-speed filter paper. The filter residue is washed twice with 2.556 L of dimethyl sulfoxide, and then washed three times with 1.704 L of deionized water. The filter residue, along with the funnel, is transferred to a vacuum drying oven and dried at 130°C for 24 hours to obtain conductive carbon black sub-product 11.

[0234] A 3L round-bottom flask equipped with a magnetic stirrer was fixed on a magnetic stirring table with heating function. 1000g of a 0.75mol / L sodium carbonate dibutylamine solution was added to the round-bottom flask. The stirrer was started at 300rpm. The temperature was maintained within the range of 25±1℃. 100g of conductive carbon black sub-product 11 was added to the round-bottom flask. The temperature was raised to 50℃ and the stirring speed was maintained, and stirring was continued for 24h. After the reaction was completed, the mixture was filtered using a vacuum filtration flask. All the material in the round-bottom flask was slowly poured into a G4 sintered glass funnel covered with medium-speed filter paper. The filter residue was washed three times with 2.608L of petroleum ether, and then three times with 2.608L of deionized water. The filter residue, along with the funnel, was transferred to a vacuum drying oven and dried at 100℃ for 24h to obtain conductive carbon black product 11.

[0235] This embodiment also provides a performance test experiment on the above-mentioned conductive carbon black finished product for soft-pack batteries. The test methods and results are as follows:

[0236] The conductive carbon black finished product 11 and the raw carbon black 11 were respectively assembled into 15 cells according to the soft-pack battery formula five for performance testing. The results are shown in [link to results]. Figures 1 to 6 .

[0237] At 20℃, the average discharge capacity of the three 0.2C pouch cells based on conductive carbon black product 11 is 1.515Ah, and the average DC internal resistance is 4.19mΩ. The average discharge capacity of the three 0.2C pouch cells based on raw carbon black 11 is 1.513Ah, and the average DC internal resistance is 4.18mΩ. At -20℃, the average discharge capacity of the three 0.2C pouch cells based on conductive carbon black product 11 is 1.106Ah, and the average discharge capacity of the three 0.2C pouch cells based on raw carbon black 11 is 1.102Ah. At 20℃, the average discharge capacity of the three 1C pouch cells based on conductive carbon black product 11 is 1.386Ah, and the average discharge capacity of the three 1C pouch cells based on raw carbon black 11 is 1.392Ah.

[0238] At 20℃, after 1169, 1174, and 1161 charge-discharge cycles respectively, the discharge capacity retention rate of three pouch cells based on conductive carbon black product 11 decreased to 70%. After 852, 846, and 848 charge-discharge cycles respectively, the discharge capacity retention rate of three pouch cells based on raw carbon black 11 decreased to 70%. The average cycle life of the cells based on conductive carbon black product 11 increased by 37.63%. After 750 cycles, the average DC internal resistance of the cells based on conductive carbon black product 11 was 15.77 mΩ, and the average DC internal resistance of the cells based on raw carbon black 11 was 19.61 mΩ.

[0239] Example 12

[0240] This embodiment provides a conductive carbon black, the preparation method of which includes:

[0241] A 2L round-bottom flask equipped with a magnetic stirrer was transferred to an argon-atmosphere glove box and fixed on a heated magnetic stirring table. 1.113L of dried methyl ethyl ketone (MEK) with a water content of 33ppm was added to the round-bottom flask. 100g of raw carbon black 12, dried at 145°C for 24h, was added to the round-bottom flask. The stirrer was started at 720rpm. The temperature was maintained within the range of 25±1°C. After five minutes, 3.196g of liquid bromine was added dropwise to the round-bottom flask using a syringe. In this embodiment, the ratio of the weight of raw carbon black 12 to the molar number of halogen atoms in the liquid bromine was 1:0.4, and the raw carbon black accounted for 10% of the total mass of raw carbon black, halogenating reagent, and solvent. After the halogenating reagent was added, the temperature and stirring speed were maintained, and stirring continued for 12h. After the reaction was completed, the mixture was filtered using a vacuum filtration flask in a glove box. All the material in the round-bottom flask was slowly poured into a G4 sintered glass funnel lined with medium-speed filter paper. The filter residue was washed three times with 2.782 L of butanone. The filter residue, along with the funnel, was transferred to a vacuum drying oven and dried at 50 °C for 12 h to obtain conductive carbon black precursor 12.

[0242] An 8L round-bottom flask equipped with a magnetic stirrer was transferred to an argon-atmospheric glove box and fixed on a heated magnetic stirring table. 4.2L of dried dichloromethane with a water content of 23ppm was added to the round-bottom flask. 29.466g of trimethylsilylacetylene was added to the round-bottom flask. The stirrer was started at 600rpm. The temperature was maintained at 25±1℃. After five minutes, 67.998g of cuprous selenide was added to the round-bottom flask. In this example, the molar ratio of carbon black acetylation reagent to cuprous salt was 1:1.1, and the total concentration of carbon black acetylation reagent and cuprous salt in the solution was 0.15mol / L. After the cuprous selenide was added, the temperature was raised to 45℃ and stirring was continued for 36 hours. After the reaction was completed, the mixture was filtered using a vacuum filtration flask in a glove box. All the material in the round-bottom flask was slowly poured into a G4 sintered glass funnel lined with medium-speed filter paper. The filter residue was washed three times with 8.4 L of dichloromethane. The filter residue, along with the funnel, was transferred to a vacuum drying oven and dried at 50°C for 12 hours to obtain activated acetylation reagent 12.

[0243] Transfer a 1.5L round-bottom flask equipped with a magnetic stirrer to an argon-atmosphere glove box and secure it to a heated magnetic stirring table. Add 694mL of dried dimethyl sulfoxide (DMSO) with a water content of 37ppm to the round-bottom flask. Add 139mL of dried tetraethylethylenediamine (TEED) with a water content of 45ppm to the round-bottom flask. Add 0.911g of bis(diphenylphosphine)ferrocene palladium dichloride and 0.756g of tri-tert-butylphosphine to the round-bottom flask. Start the stirrer at 600rpm. Maintain the temperature within the range of 25±1℃. After three minutes, add 100g of conductive carbon black precursor 12 to the round-bottom flask. Add 20.894g of activated acetylation reagent 12 to the round-bottom flask. In this embodiment, the volume ratio of the aprotic solvent to the organic tertiary amine is 1:0.2, the molar ratio of the catalyst to the co-catalyst is 1:3, the ratio of the kilogram of the conductive carbon black precursor to the molar amount of the activated acetylation reagent is 1:1.3, the total mass ratio of the catalyst and co-catalyst to the conductive carbon black precursor is 1:60, and the mass percentage of the conductive carbon black precursor in the total reaction system is 10%. After the activated acetylation reagent is added, the temperature is raised to 150°C and stirred continuously for 24 hours. After the reaction is completed, the mixture is filtered in a glove box using a vacuum filtration flask. All the material in the round-bottom flask is slowly poured into a G4 sintered glass funnel covered with medium-speed filter paper. The filter residue is washed twice with 2.499 L of dimethyl sulfoxide, and then washed three times with 1.666 L of deionized water. The filter residue, along with the funnel, is transferred to a vacuum drying oven and dried at 150°C for 24 hours to obtain conductive carbon black sub-product 12.

[0244] A 3L round-bottom flask equipped with a magnetic stirrer was fixed on a magnetic stirring table with heating function. 1000g of a 0.75mol / L sodium carbonate dibutylamine solution was added to the round-bottom flask. The stirrer was started at 300rpm. The temperature was maintained within the range of 25±1℃. 100g of conductive carbon black sub-product 12 was added to the round-bottom flask. The temperature was raised to 50℃ and the stirring speed was maintained, and stirring was continued for 24h. After the reaction was completed, the mixture was filtered using a vacuum filtration flask. All the material in the round-bottom flask was slowly poured into a G4 sintered glass funnel covered with medium-speed filter paper. The filter residue was washed three times with 2.608L of petroleum ether, and then three times with 2.608L of deionized water. The filter residue, along with the funnel, was transferred to a vacuum drying oven and dried at 100℃ for 24h to obtain conductive carbon black product 12.

[0245] This embodiment also provides a performance test experiment on the above-mentioned conductive carbon black finished product for soft-pack batteries. The test methods and results are as follows:

[0246] The conductive carbon black finished product 12 and the raw carbon black 12 were respectively assembled into 15 cells according to the soft-pack battery formula six for performance testing. The results are shown in [link to results]. Figures 1 to 6 .

[0247] At 20℃, the average discharge capacity of the three 0.2C pouch cells based on conductive carbon black product 12 is 1.512Ah, and the average DC internal resistance is 4.18mΩ. The average discharge capacity of the three 0.2C pouch cells based on raw carbon black 12 is 1.521Ah, and the average DC internal resistance is 4.21mΩ. At -20℃, the average discharge capacity of the three 0.2C pouch cells based on conductive carbon black product 12 is 1.106Ah, and the average discharge capacity of the three 0.2C pouch cells based on raw carbon black 12 is 1.109Ah. At 20℃, the average discharge capacity of the three 1C pouch cells based on conductive carbon black product 12 is 1.399Ah, and the average discharge capacity of the three 1C pouch cells based on raw carbon black 12 is 1.396Ah.

[0248] At 20℃, after 1211, 1204, and 1198 charge-discharge cycles respectively, the discharge capacity retention rate of three pouch cells based on conductive carbon black product 12 decreased to 70%. After 861, 859, and 848 charge-discharge cycles respectively, the discharge capacity retention rate of three pouch cells based on raw carbon black 12 decreased to 70%. The average cycle life of the cells based on conductive carbon black product 12 increased by 40.69%. After 750 cycles, the average DC internal resistance of the cells based on conductive carbon black product 12 was 16.6 mΩ, and the average DC internal resistance of the cells based on raw carbon black 12 was 19.4 mΩ.

[0249] Example 13

[0250] This embodiment provides a conductive carbon black, the preparation method of which includes:

[0251] A 2L round-bottom flask equipped with a magnetic stirrer was transferred to an argon-atmosphere glove box and fixed on a heated magnetic stirring table. 1.133L of dried acetonitrile with a moisture content of 36ppm was added to the round-bottom flask. 100g of raw carbon black 13, dried at 160℃ for 24h, was added to the round-bottom flask. The stirrer was started at 360rpm. The temperature was maintained within the range of 25±1℃. After five minutes, 9.789g of N-bromosuccinimide was slowly added to the round-bottom flask using a spatula. In this embodiment, the ratio of the weight of raw carbon black 13 to the molar number of halogen atoms in N-bromosuccinimide was 1:0.55, and the raw carbon black accounted for 10% of the total mass of raw carbon black, halogenating reagent, and solvent. After the halogenating reagent was added, the temperature was raised to 70℃ and stirring was continued for 48h. After the reaction was completed, the mixture was filtered using a vacuum filtration flask in a glove box. All the material in the round-bottom flask was slowly poured into a G4 sintered glass funnel lined with medium-speed filter paper. The filter residue was washed three times with 3.398 L of acetonitrile. The filter residue, along with the funnel, was transferred to a vacuum drying oven and dried at 50 °C for 12 h to obtain conductive carbon black precursor 13.

[0252] A 1.5L round-bottom flask equipped with a magnetic stirrer was transferred to an argon-atmosphere glove box and fixed on a heated magnetic stirring table. 660mL of dried dioxane with a water content of 41ppm was added to the round-bottom flask. 31.245g of trimethylsilylacetylene was added to the round-bottom flask. The stirrer was started at 240rpm. The temperature was maintained at 25±1℃. After five minutes, 51.642g of cuprous bromide was added to the round-bottom flask. In this example, the molar ratio of carbon black acetylation reagent to cuprous salt was 1:1.2, and the total concentration of carbon black acetylation reagent and cuprous salt in the solution was 1mol / L. After the cuprous bromide was added, the temperature was raised to 80℃ and stirring was continued for 36 hours. After the reaction was completed, the mixture was filtered using a vacuum filtration flask in a glove box. All the material in the round-bottom flask was slowly poured into a G4 sintered glass funnel lined with medium-speed filter paper. The filter residue was rinsed three times with 1.65 L of dioxane. The filter residue, along with the funnel, was transferred to a vacuum drying oven and dried at 70°C for 18 hours to obtain activated acetylation reagent 13.

[0253] Transfer a 1.5L round-bottom flask equipped with a magnetic stirrer to an argon-atmosphere glove box and secure it to a heated magnetic stirring table. Add 694mL of dried dimethyl sulfoxide (DMSO) with a water content of 37ppm to the round-bottom flask. Add 139mL of dried tetraethylethylenediamine (TEED) with a water content of 45ppm to the round-bottom flask. Add 1.481g of tetra(triphenylphosphine)palladium and 0.519g of tritert-butylphosphine to the round-bottom flask. Start the stirrer at 600rpm. Maintain the temperature within the range of 25±1℃. After three minutes, add 100g of conductive carbon black precursor 13 to the round-bottom flask. Add 22.501g of activated acetylation reagent 13 to the round-bottom flask. In this embodiment, the volume ratio of the aprotic solvent to the organic tertiary amine is 1:0.2, the molar ratio of the catalyst to the co-catalyst is 1:2, the ratio of the kilogram of the conductive carbon black precursor to the molar amount of the activated acetylation reagent is 1:1.4, the total mass ratio of the catalyst and co-catalyst to the conductive carbon black precursor is 1:50, and the mass percentage of the conductive carbon black precursor in the total reaction system is 10%. After the activated acetylation reagent is added, the temperature is raised to 150°C and stirred continuously for 24 hours. After the reaction is completed, the mixture is filtered in a glove box using a vacuum filtration flask. All the material in the round-bottom flask is slowly poured into a G4 sintered glass funnel covered with medium-speed filter paper. The filter residue is washed twice with 2.499 L of dimethyl sulfoxide, and then washed three times with 1.666 L of deionized water. The filter residue, along with the funnel, is transferred to a vacuum drying oven and dried at 150°C for 24 hours to obtain conductive carbon black sub-product 13.

[0254] A 3L round-bottom flask equipped with a magnetic stirrer was fixed on a magnetic stirring table with heating function. 1000g of a 0.5mol / L diisopropylamine solution of potassium carbonate was added to the round-bottom flask. The stirrer was started at 300rpm. The temperature was maintained within the range of 25±1℃. 100g of conductive carbon black sub-product 13 was added to the round-bottom flask. The temperature was raised to 85℃ and the stirring speed was maintained for 24 hours. After the reaction was completed, the mixture was filtered using a vacuum filtration flask. All the material in the round-bottom flask was slowly poured into a G4 sintered glass funnel covered with medium-speed filter paper. The filter residue was washed three times with 2.778L of diisopropylamine, and then three times with 2.778L of deionized water. The filter residue, along with the funnel, was transferred to a vacuum drying oven and dried at 100℃ for 24 hours to obtain conductive carbon black product 13.

[0255] This embodiment also provides a performance test experiment on the above-mentioned conductive carbon black finished product for soft-pack batteries. The test methods and results are as follows:

[0256] The conductive carbon black finished product 13 and the raw carbon black 13 were respectively assembled into 15 cells according to the soft-pack battery formula five for performance testing. The results are shown in [link to results]. Figures 1 to 6 .

[0257] At 20℃, the average discharge capacity of the three 0.2C pouch cells based on conductive carbon black product 13 is 1.509Ah, and the average DC internal resistance is 4.27mΩ. The average discharge capacity of the three 0.2C pouch cells based on raw carbon black 13 is 1.502Ah, and the average DC internal resistance is 4.26mΩ. At -20℃, the average discharge capacity of the three 0.2C pouch cells based on conductive carbon black product 13 is 1.111Ah, and the average discharge capacity of the three 0.2C pouch cells based on raw carbon black 13 is 1.108Ah. At 20℃, the average discharge capacity of the three 1C pouch cells based on conductive carbon black product 13 is 1.415Ah, and the average discharge capacity of the three 1C pouch cells based on raw carbon black 13 is 1.42Ah.

[0258] At 20℃, after 1201, 1193, and 1237 charge-discharge cycles respectively, the discharge capacity retention rate of three pouch cells based on conductive carbon black product 13 decreased to 70%. After 853, 861, and 846 charge-discharge cycles respectively, the discharge capacity retention rate of three pouch cells based on raw carbon black 13 decreased to 70%. The average cycle life of the cells based on conductive carbon black product 13 increased by 41.84%. After 750 cycles, the average DC internal resistance of the cells based on conductive carbon black product 13 was 15.21 mΩ, and the average DC internal resistance of the cells based on raw carbon black 13 was 19.67 mΩ.

[0259] Example 14

[0260] This embodiment provides a conductive carbon black, the preparation method of which includes:

[0261] A 2L round-bottom flask equipped with a magnetic stirrer was transferred to an argon-atmosphere glove box and fixed on a heated magnetic stirring table. 859mL of dried dioxane with a moisture content of 40ppm was added to the round-bottom flask. 100g of raw carbon black 14, dried at 160℃ for 24h, was added to the round-bottom flask. The stirrer was started at 360rpm. The temperature was maintained within the range of 25±1℃. After five minutes, 11.925g of N-bromosuccinimide was slowly added to the round-bottom flask using a spatula. In this embodiment, the ratio of the weight of raw carbon black 14 to the molar number of halogen atoms in N-bromosuccinimide was 1:0.67, and the raw carbon black accounted for 10% of the total mass of raw carbon black, halogenating reagent, and solvent. After the halogenating reagent was added, the temperature was raised to 100℃ and stirring was continued for 48h. After the reaction was completed, the mixture was filtered using a vacuum filtration flask in a glove box. All the material in the round-bottom flask was slowly poured into a G4 sintered glass funnel lined with medium-speed filter paper. The filter residue was washed three times with 2.577 L of dioxane. The filter residue, along with the funnel, was transferred to a vacuum drying oven and dried at 70 °C for 18 h to obtain conductive carbon black precursor 14.

[0262] A 2L round-bottom flask equipped with a magnetic stirrer was transferred to an argon-atmosphere glove box and fixed on a heated magnetic stirring table. 825mL of dried dioxane with a water content of 41ppm was added to the round-bottom flask. 31.245g of trimethylsilylacetylene was added to the round-bottom flask. The stirrer was started at 240rpm. The temperature was maintained within the range of 25±1℃. After five minutes, 35.64g of cuprous chloride was added to the round-bottom flask. In this example, the molar ratio of carbon black acetylation reagent to cuprous salt was 1:1.2, and the total concentration of carbon black acetylation reagent and cuprous salt in the solution was 0.8mol / L. After the cuprous chloride was added, the temperature was raised to 100℃ and stirring was continued for 36 hours. After the reaction was completed, the mixture was filtered using a vacuum filtration flask in a glove box. All the material in the round-bottom flask was slowly poured into a G4 sintered glass funnel lined with medium-speed filter paper. The filter residue was rinsed three times with 2.064 L of dioxane. The filter residue, along with the funnel, was transferred to a vacuum drying oven and dried at 70°C for 18 hours to obtain activated acetylation reagent 14.

[0263] Transfer a 1.5L round-bottom flask equipped with a magnetic stirrer to an argon-atmosphere glove box and secure it to a heated magnetic stirring table. Add 694mL of dried dimethyl sulfoxide (DMSO) with a water content of 37ppm to the round-bottom flask. Add 139mL of dried tetraethylethylenediamine (TEDE) with a water content of 45ppm to the round-bottom flask. Add 0.929g of bis(triphenylphosphine)palladium dichloride and 1.071g of tritert-butylphosphine to the round-bottom flask. Start the stirrer at 600rpm. Maintain the temperature within the range of 25±1℃. After three minutes, add 100g of conductive carbon black precursor 14 to the round-bottom flask. Add 24.108g of activated acetylation reagent 14 to the round-bottom flask. In this embodiment, the volume ratio of the aprotic solvent to the organic tertiary amine is 1:0.2, the molar ratio of the catalyst to the co-catalyst is 1:4, the ratio of the kilogram of the conductive carbon black precursor to the molar amount of the activated acetylation reagent is 1:1.5, the total mass ratio of the catalyst and co-catalyst to the conductive carbon black precursor is 1:50, and the mass percentage of the conductive carbon black precursor in the total reaction system is 10%. After the activated acetylation reagent is added, the temperature is raised to 150°C and stirred continuously for 24 hours. After the reaction is completed, the mixture is filtered in a glove box using a vacuum filtration flask. All the material in the round-bottom flask is slowly poured into a G4 sintered glass funnel covered with medium-speed filter paper. The filter residue is washed twice with 2.499 L of dimethyl sulfoxide, and then washed three times with 1.666 L of deionized water. The filter residue, along with the funnel, is transferred to a vacuum drying oven and dried at 150°C for 24 hours to obtain conductive carbon black sub-product 14.

[0264] A 3L round-bottom flask equipped with a magnetic stirrer was fixed on a magnetic stirring table with heating function. 1000g of a 0.5mol / L potassium carbonate diisopropylamine solution was added to the round-bottom flask. The stirrer was started at 300rpm. The temperature was maintained within the range of 25±1℃. 100g of conductive carbon black sub-product 14 was added to the round-bottom flask. The temperature was raised to 85℃ and the stirring speed was maintained for 24 hours. After the reaction was completed, the mixture was filtered using a vacuum filtration flask. All the material in the round-bottom flask was slowly poured into a G4 sintered glass funnel covered with medium-speed filter paper. The filter residue was washed three times with 2.778L of petroleum ether, and then three times with 2.778L of deionized water. The filter residue, along with the funnel, was transferred to a vacuum drying oven and dried at 100℃ for 24 hours to obtain conductive carbon black product 14.

[0265] This embodiment also provides a performance test experiment on the above-mentioned conductive carbon black finished product for soft-pack batteries. The test methods and results are as follows:

[0266] The conductive carbon black finished product 14 and the raw carbon black 14 were respectively assembled into 15 cells according to the soft-pack battery formula six for performance testing. The results are shown in [link to results]. Figures 1 to 6 .

[0267] At 20℃, the average discharge capacity of the three 0.2C pouch cells based on conductive carbon black product 14 is 1.517Ah, and the average DC internal resistance is 4.23mΩ. The average discharge capacity of the three 0.2C pouch cells based on raw carbon black 14 is 1.508Ah, and the average DC internal resistance is 4.22mΩ. At -20℃, the average discharge capacity of the three 0.2C pouch cells based on conductive carbon black product 14 is 1.121Ah, and the average discharge capacity of the three 0.2C pouch cells based on raw carbon black 14 is 1.116Ah. At 20℃, the average discharge capacity of the three 1C pouch cells based on conductive carbon black product 14 is 1.402Ah, and the average discharge capacity of the three 1C pouch cells based on raw carbon black 14 is 1.411Ah.

[0268] At 20℃, after 1274, 1258, and 1217 charge-discharge cycles respectively, the discharge capacity retention rate of three pouch cells based on conductive carbon black product 14 decreased to 70%. After 903, 917, and 908 charge-discharge cycles respectively, the discharge capacity retention rate of three pouch cells based on raw carbon black 14 decreased to 70%. The average cycle life of the cells based on conductive carbon black product 14 increased by 37.43%. After 750 cycles, the average DC internal resistance of the cells based on conductive carbon black product 14 was 15.48 mΩ, and the average DC internal resistance of the cells based on raw carbon black 14 was 19.5 mΩ.

[0269] As can be seen from the examples, the conductive carbon black produced by this invention, when applied to lithium batteries, can significantly improve the cycle life of the battery without affecting parameters such as room temperature discharge capacity, low temperature discharge capacity, and high-rate discharge capacity at room temperature. This improvement in cycle life is applicable to carbon black raw materials and battery materials with different properties.

[0270] The foregoing has provided detailed and specific implementation examples of the present invention. However, it should be noted that we can make various equivalent changes and modifications to the above implementation examples in accordance with the concept of the present invention. As long as the resulting functions do not exceed the spirit of the specification, they should all be within the protection scope of the present invention.

Claims

1. A method for preparing conductive carbon black, the method comprising: S1. Mix raw carbon black and halogenating reagent, and perform halogenation treatment in a protective atmosphere to obtain conductive carbon black precursor. S2. Mix carbon black acetylation reagent and cuprous salt, and activate them in a protective atmosphere to obtain activated acetylation reagent. S3. The activated acetylation reagent and the conductive carbon black precursor are mixed and subjected to carbon black acetylation treatment in a protective atmosphere to obtain conductive carbon black sub-product. The conductive carbon black sub-product is subjected to deprotection treatment to obtain conductive carbon black.

2. The preparation method according to claim 1, wherein, The raw material carbon black satisfies one or more of the following conditions: The specific surface area of ​​the raw material carbon black is 120-560 m². 2 / g; The oil absorption value of the raw material carbon black is 130-330cc / 100g; The graphitization degree of the raw material carbon black is 20%-42%; The iron content of the raw material carbon black is 0ppm-10ppm; The total content of nickel, cobalt, manganese, zinc, copper and chromium in the raw carbon black is 0ppm-5ppm; The sulfur content of the raw material carbon black is 0ppm-800ppm.

3. The preparation method according to claim 1, wherein, The halogenating agent includes one or more of the following: iodine chloride, a mixture of mercuric iodide and mercuric oxide, N-iodosuccinimide, elemental bromine, and N-bromosuccinimide.

4. The preparation method according to claim 1, wherein, The ratio of the mass of the raw material carbon black to the molar mass of the halogen atom of the halogenating reagent is 1 kg : (0.1-0.67) mol.

5. The preparation method according to claim 1, wherein, The raw material carbon black is mixed with the halogenating reagent in a first solvent to form a halogenated raw material solution, and then subjected to halogenation treatment; the first solvent is an aprotic solvent.

6. The preparation method according to claim 5, wherein, The mass of the raw carbon black is 10%-25% of the total mass of the raw carbon black, halogenating reagent, and first solvent.

7. The preparation method according to claim 1, wherein, In S1, the reaction temperature of the halogenation treatment is 25-125℃, and the reaction time of the halogenation treatment is 12h-48h.

8. The preparation method according to claim 1, wherein, The carbon black acetylation reagent includes one or more of the following: trimethylsilylacetylene, lithium trimethylsilylacetylene, triethylsilylacetylene, tert-butyldimethylsilylacetylene, triisopropylsilylacetylene, dimethylphenylsilylacetylene, and triphenylsilylacetylene.

9. The preparation method according to claim 1, wherein, The cuprous salt includes one or more of the following: cuprous iodide, cuprous bromide, cuprous chloride, cuprous sulfide, cuprous oxide, cuprous thiocyanate, cuprous acetate, cuprous selenide, and cuprous cyanide.

10. The preparation method according to claim 1, wherein, The molar ratio of the carbon black acetylation reagent to the cuprous salt is 1:(1.05-1.4).

11. The preparation method according to claim 1, wherein, In S2, the carbon black acetylation reagent and the cuprous salt are mixed in a second solvent to form an activated raw material solution, which is then activated. The second solvent is an aprotic solvent.

12. The preparation method according to claim 11, wherein, In S2, the total concentration of the carbon black acetylation reagent and cuprous salt in the activated raw material solution is 0.15-2 mol / L.

13. The preparation method according to claim 1, wherein, The activation treatment temperature is 25-100℃, and the activation treatment time is 24h-48h.

14. The preparation method according to claim 1, wherein, The mass ratio of the conductive carbon black precursor to the molar amount of the activated acetylation reagent is 1 kg : (0.07-1.5) mol.

15. The preparation method according to claim 1, wherein, In S3, the carbon black acetylation process uses a main catalyst for catalysis, and the main catalyst includes a palladium-based catalyst. The carbon black acetylation process also uses a co-catalyst, which is a phosphorus-containing compound. The molar ratio of the main catalyst to the co-catalyst is 1:(1-4); The total mass ratio of the main catalyst and the co-catalyst to the mass ratio of the conductive carbon black precursor is 1:(50-230).

16. The preparation method according to claim 15, wherein, The palladium-based catalyst includes one or more of the following: palladium trifluoroacetate, palladium acetate, palladium tetratriphenylphosphine, palladium dichlorobis(triphenylphosphine), palladium [bis(diphenylphosphine)ferrocene] dichloride, palladium bis(acetonitrile) dichloride, palladium bis(tricyclohexylphosphine) dichloride, palladium hexafluoroacetylacetonate, palladium (1,5-cyclooctadiene) dichloride, palladium bis(dibenzylacetone), palladium [1,2-bis(diphenylphosphine)ethane] dichloride, palladium dichlorobis(tri-o-toluene) dichloride, palladium (2,2'-bipyridine) dichloride, palladium dichloride bis(cyanobenzene) dichloride, and palladium bis(diphenylacetone). The phosphorus-containing compound includes one or more of the following: triphenylphosphine, tricyclohexylphosphine, 2-di-tert-butylphosphine-1-phenylindole, 1,3-bis(diphenylphosphine)propane, 1,4-bis(diphenylphosphine)butane, tri-tert-butylphosphine, n-butylbis(1-adamantyl)phosphine, tris(2-furanyl)phosphine, and 2-tert-butylphosphine-1-phenylindole.

17. The preparation method according to claim 1, wherein, In S3, the activated acetylation reagent and the conductive carbon black precursor are mixed in a third solvent to form an acetylation raw material solution, and then carbon black acetylation treatment is performed. The third solvent is a combination of an aprotic solvent and an organic tertiary amine, and the volume ratio of the aprotic solvent to the organic tertiary amine is 1:0.05-0.

33.

18. The preparation method according to claim 17, wherein, The conductive carbon black precursor has a mass percentage of 10%-28% in the acetylation feedstock solution.

19. The preparation method according to claim 1, wherein, The temperature for the carbon black acetylation treatment is 50-180℃, and the time for the carbon black acetylation treatment is 6h-24h.

20. The preparation method according to claim 1, wherein, The deprotection treatment includes: mixing the pressed conductive carbon black product with an alkaline solution for deprotection treatment to obtain the finished conductive carbon black product; The concentration of the alkaline solution is 0.5-2.5 mol / L, and the mass ratio of the carbon black sub-finished product to the alkaline solution is 1:(1.5-10).

21. The preparation method according to claim 1, wherein, The temperature for the deprotection treatment is 25-100℃, and the time for the deprotection treatment is 12h-48h.

22. A conductive carbon black, which is obtained by the method for preparing conductive carbon black according to any one of claims 1-21.

23. The conductive carbon black according to claim 22, wherein, The specific surface area of ​​the conductive carbon black is 120-560 m². 2 / g; And / or, the oil absorption value of the conductive carbon black is 120-330cc / 100g; And / or, the degree of graphitization of the conductive carbon black is 20%-42%; And / or, the acetylation content in the conductive carbon black is 30-500 mmol / kg carbon black; And / or, the acetylation content in the conductive carbon black is 0.2-1.4 μmol / m 2 Carbon black.

24. A lithium battery, wherein the raw material of the lithium battery comprises the conductive carbon black as described in any one of claims 22-23.

25. The lithium battery according to claim 24, wherein the lithium battery comprises a positive electrode, a negative electrode, and an ion transport medium; The positive electrode is made of a positive electrode active material, a conductive agent, and a binder, wherein the conductive agent includes the conductive carbon black according to any one of claims 22-23.

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