CN112542590A - Easily-dispersible carbon black conductive agent and preparation method and application thereof - Google Patents
Easily-dispersible carbon black conductive agent and preparation method and application thereof Download PDFInfo
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- CN112542590A CN112542590A CN202011431393.3A CN202011431393A CN112542590A CN 112542590 A CN112542590 A CN 112542590A CN 202011431393 A CN202011431393 A CN 202011431393A CN 112542590 A CN112542590 A CN 112542590A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to an easily dispersible carbon black conductive agent and a preparation method and application thereof; the easily-dispersible carbon black conductive agent comprises carbon black and carboxymethyl cellulose grafted on the surface of the carbon black, and the carboxymethyl cellulose grafted on the surface of the carbon black has better solubility in water, so that the easily-dispersible carbon black conductive agent is favorable for preventing the carbon black from agglomerating and forming lithium ion battery slurry with the conductive agent well dispersed; the easily-dispersible carbon black conductive agent is used for lithium ion battery slurry, and compared with the traditional carbon black, the easily-dispersible carbon black conductive agent can reduce the internal resistance of a lithium ion battery and further improve the rate capability of the lithium ion battery.
Description
Technical Field
The invention belongs to the field of lithium ion batteries, and relates to an easily dispersible carbon black conductive agent, and a preparation method and application thereof.
Background
Carbon black is the most widely used conductive agent in the lithium ion battery, the dispersion quality of the carbon black affects the internal resistance of the lithium ion battery, especially in a high-power battery, on one hand, the internal resistance has a large influence on the rate performance, and on the other hand, the addition amount of the conductive agent in the formula of the high-power battery is large, so that the dispersion is more difficult; at present, few reports are provided in the field of lithium ion batteries for the preparation of easily dispersible carbon black conductive agents. At present, the modification of carbon black mainly focuses on the fields of rubber, printing ink, conductive polymer and film manufacturing and the like. Some polymers introduced in the fields of rubber, ink and the like are not suitable for the field of batteries, and the polymer molecular weight introduced in the preparation of conductive polymers partially used for batteries is larger, the amount of carbon black is less, and the polymer is not suitable for being added in a large amount to serve as a conductive agent in high-power batteries.
CN107658429A discloses a preparation method of lithium ion battery slurry, which comprises the following steps: s1: adding a solvent which accounts for 2-10% of the mass of the battery active substance into the battery active substance, and uniformly stirring to obtain a first product; s2: adding a first binder and a part of solvent into the first product obtained in the step S1, and uniformly stirring to obtain a second product; the concentration of the second product is 5-12%; s3: adding a conductive agent into the second product obtained in the step S2, and uniformly stirring to obtain a third product; s4: adding a second binder and the rest solvent into the third product obtained in the step S3, and stirring to obtain the final lithium ion battery slurry, wherein the conductive agent is one or more of carbon black, carbon fibers, carbon nanotubes and graphite; CN102738446A discloses a preparation method of lithium ion battery slurry, which comprises the following steps: step one, preparing glue solution with the concentration of 3% -7% by using an adhesive; step two, uniformly mixing the active substance and the conductive agent in a three-arm planetary mixer at a low speed to form powder; step three, adding 1% -15% of the total amount of the solvent into the powder in the step two, and uniformly mixing at a low speed to form wet powder, wherein the mass ratio of the total amount of the solvent to the powder is 55: 4-50: 50; step four, adding 20-50% of glue solution and the rest solvent into the wet powder in the step three, and uniformly mixing at a high speed; step five, adding the rest glue solution, uniformly stirring for 5-10 minutes at a low speed, and then stirring for 2-5 hours at a high speed to form lithium ion battery slurry, wherein the conductive agent is one of carbon black, carbon fibers, carbon nanotubes and graphite; in the above schemes, carbon black is used as the conductive agent, which has the problem of carbon black dispersion uniformity, and especially in the high-power lithium ion battery, when the addition amount of the conductive agent is high, the dispersion performance of the conductive agent has a greater influence on the internal resistance and the cycle performance of the battery.
Therefore, the development of the modified carbon black conductive agent with good dispersibility in the battery slurry has important significance for improving the performance of the lithium ion battery, especially the high-power lithium ion battery.
Disclosure of Invention
The invention aims to provide an easily dispersible carbon black conductive agent, a preparation method and application thereof; the easily-dispersible carbon black conductive agent comprises carbon black and carboxymethyl cellulose grafted on the surface of the carbon black, and the carboxymethyl cellulose grafted on the surface of the carbon black has better solubility in water, so that the easily-dispersible carbon black conductive agent is favorable for preventing the carbon black from agglomerating and forming lithium ion battery slurry with the conductive agent well dispersed; the easily-dispersible carbon black conductive agent is used for lithium ion battery slurry, and compared with the traditional carbon black, the easily-dispersible carbon black conductive agent can reduce the internal resistance of a lithium ion battery and further improve the rate capability of the lithium ion battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides an easily dispersible carbon black conductive agent, which includes carbon black and carboxymethyl cellulose grafted on the surface of the carbon black.
The uniformity of the dispersion of the conductive agent has great influence on the internal resistance of the lithium ion battery, particularly has more remarkable influence in a high-power lithium ion battery, and the dispersion of the conductive agent can cause the internal resistance of the battery to be overlarge, so that the rate performance is reduced, and the performance of the battery is influenced; the invention mainly solves the problems that the conductive agent in the formula of the high-power lithium ion battery is difficult to disperse, so that the internal resistance of the battery is too high and the multiplying power performance of the battery is reduced. Based on the fact that the carbon black is used as the most widely used conductive agent in the lithium ion battery, the surface of the carbon black in the easily-dispersible carbon black conductive agent is grafted with the carboxymethyl cellulose, the easily-dispersible carbon black conductive agent has good solubility in water, and the easily-dispersible carbon black conductive agent can prevent the carbon black from agglomerating to further form well-dispersed lithium ion battery slurry; compared with the traditional carbon black, the internal resistance of the high-power lithium battery prepared from the carbon black is obviously reduced, and the rate capability of the high-power lithium battery is also obviously improved.
Preferably, the carboxymethyl cellulose has a molecular weight of 3 to 8 ten thousand, such as 3 ten thousand, 4 ten thousand, 5 ten thousand, 6 ten thousand, 7 ten thousand, or 8 ten thousand, and the like.
Preferably, the specific surface area of the easily dispersible carbon black conductive agent is 90-130m2In g, e.g. 90m2/g、100m2/g、110m2/g、120m2G or 130m2And/g, etc.
Preferably, the mass ratio of the carbon black to the carboxymethyl cellulose in the easily dispersible carbon black conductive agent is 1: 0.1.
The easy dispersion means that the modified carbon black conductive agent has better dispersion performance in slurry than the traditional carbon black.
The raw material of the easily dispersible carbon black conductive agent comprises virgin carbon black.
Preferably, the primary carbon black has a particle size of 10-30nm, such as 12nm, 15nm, 18nm, 20nm, 22nm, 25nm, 28nm, or the like.
The particle size of the primary carbon black is 10-30nm, and the primary carbon black has better dispersibility in slurry after being grafted, so that the internal resistance of a high-power lithium ion battery is favorably reduced, and when the particle size is too small, the specific surface area of the carbon black is very large, and the surface energy is too high, so that agglomeration is easily generated, and the dispersibility is difficult to improve by using the modification method provided by the invention; when the particle size is too large, the specific surface area of the carbon black is too small, the graphitization degree of the carbon black is also small, the conductivity of the carbon black is not good, and the reduction of the internal resistance of the battery is not facilitated.
Preferably, the specific surface area of the raw carbon black is 60 to 300m2In g, e.g. 80m2/g、100m2/g、120m2/g、150m2/g、180m2/g、200m2/g、220m2/g、240m2/g、260m2/g or 280m2And/g, etc.
The specific surface area of the raw carbon black is 60-300m2The carboxymethyl cellulose grafted on the carbon black has better dispersibility in slurry, when the specific surface area is too small, the graphitization degree of the carbon black is also smaller, the conductivity of the carbon black is not good, and the reduction of the internal resistance of the battery is not facilitated; the surface energy is too high, agglomeration is easy to generate, and the modification method provided by the invention is difficult to improve the dispersibility.
In a second aspect, the present invention provides a method for preparing the easily dispersible carbon black conductive agent according to the first aspect, comprising the steps of:
(1) oxidizing the primary carbon black to obtain oxidized carbon black;
(2) introducing acyl chloride groups on the surface of the oxidized carbon black in the step (1) to obtain acyl chloride carbon black;
(3) and (3) reacting the acyl chloride carbon black in the step (2) with carboxymethyl cellulose to obtain the easily dispersible carbon black conductive agent.
The virgin carbon black herein refers to carbon black for a lithium ion battery conductive agent, which has not been treated by the method of the present invention.
In the invention, the surface oxidation is carried out on the primary carbon black to obtain the oxidized carbon black. The purpose of oxidation is to increase carboxylic acid oxygen-containing functional groups on the surface of the carbon black, so that the carboxylic acid oxygen-containing functional groups can react with more acyl chloride groups, and the grafting rate on the surface of the carbon black can be further improved. Introducing acyl chloride groups on the surface of the obtained oxidized carbon black, and then carrying out grafting reaction with carboxymethyl cellulose to obtain the easily-dispersible carbon black conductive agent; by adopting the method, a large amount of carboxymethyl cellulose can be grafted on the surface of the carbon black, so that the requirement of the carbon black on dispersibility in the preparation process of the lithium ion battery slurry is met, and the effects of reducing the internal resistance of the battery and improving the rate capability are achieved.
Preferably, the method for oxidizing the raw carbon black in the step (1) comprises the steps of dispersing the raw carbon black in water, and introducing a gaseous oxidant to perform an oxidation reaction to obtain the oxidized carbon black.
Preferably, the gaseous oxidant comprises oxygen and/or ozone.
The surface treatment is carried out on the raw carbon black by adopting the gas oxidant, and the reason is that the gaseous oxidant can reduce the introduction of metal ion impurities and reduce the safety risk of the battery. Therefore, conventional liquid oxidizing agents such as hydrogen peroxide, nitric acid, etc. cannot be used here.
Preferably, the gaseous oxidizing agent is introduced at a rate of 1-100mL/min, such as 2mL/min, 5mL/min, 10mL/min, 20mL/min, 30mL/min, 40mL/min, 50mL/min, 60mL/min, 70mL/min, 80mL/min, or 90mL/min, and the like.
Preferably, the time of the oxidation reaction is not less than 24 hours, such as 26 hours, 28 hours, 30 hours, 35 hours, 40 hours or 50 hours, and preferably 30-40 hours.
Preferably, the temperature of the oxidation reaction is 30-80 ℃, such as 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃ or 75 ℃, preferably 40-60 ℃.
Preferably, the oxidation reaction is carried out with ultrasound.
The method aims to ensure that unmodified carbon black is easy to agglomerate, the carbon black is kept in a dispersed state by continuous ultrasonic treatment in the reaction process, and the surface is exposed to be more beneficial to the occurrence of oxidation reaction.
Preferably, the entire course of the oxidation reaction is accompanied by sonication.
Preferably, the oxidation reaction in step (1) is further followed by solid-liquid separation and drying.
Preferably, the method for introducing acyl chloride groups on the surface of the oxidized carbon black in the step (2) comprises mixing the oxidized carbon black with an acyl chlorination reagent to perform acyl chlorination reaction.
Preferably, the acid chlorination reagent comprises at least one of phosgene, oxalyl chloride, phosphorus oxychloride or phosphorus pentachloride, preferably oxalyl chloride.
Preferably, the temperature of the acyl chlorination reaction is 25-80 ℃, such as 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃ or 75 ℃ and the like, preferably 40-60 ℃, for 24-48h, such as 26h, 28h, 30h, 32h, 34h, 36h, 38h, 40h, 42h, 44h or 46h and the like.
Preferably, after the acyl chlorination reaction is finished, removing the acyl chlorination reagent to obtain the acyl chlorination carbon black.
Preferably, the method for reacting the acyl chloride carbon black with the carboxymethyl cellulose in the step (3) comprises the steps of mixing the acyl chloride carbon black, the carboxymethyl cellulose and a solvent, and carrying out a grafting reaction to obtain the easily dispersible carbon black conductive agent.
Preferably, the solvent is selected from at least one of water, chloroform, DMAC or DMF.
Preferably, the temperature of the grafting reaction is 25-80 ℃, such as 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃ or 75 ℃ and the like, preferably 40-60 ℃, for 1-24h, such as 2h, 5h, 10h, 15h or 20h and the like.
Preferably, the mass ratio of the carboxymethyl cellulose to the carbon black is 0.01-0.2:1 in the step (3); e.g., 0.02:1, 0.05:1, 0.1:1, or 0.15:1, etc.
As a preferable technical scheme of the invention, the preparation method of the easily dispersible carbon black conductive agent comprises the following steps:
(1) dispersing the original carbon black in an aqueous solution by using an ultrasonic method, introducing oxygen and/or ozone, carrying out an oxidation reaction at a temperature of between 30 and 80 ℃ for more than 24 hours, filtering and drying to obtain oxidized carbon black, wherein the introduction rate of the oxygen and/or the ozone is 1 to 100 mL/min; ultrasonic is always needed in the oxidation reaction process;
(2) adding the carbon black oxide obtained in the step (1) into an acyl chlorination reagent, carrying out acyl chlorination reaction for 24-48h at 25-80 ℃, and removing the acyl chlorination reagent to obtain the carbon black oxide, wherein the acyl chlorination reagent is selected from at least one of phosgene, oxalyl chloride, phosphorus oxychloride or phosphorus pentachloride;
(3) and (3) reacting the acyl chloride carbon black in the step (2) with carboxymethyl cellulose in a solvent to obtain the easily dispersible carbon black conductive agent, wherein the solvent is at least one of water, chloroform, DMAC (dimethylacetamide) or DMF (dimethyl formamide), the reaction temperature is 25-80 ℃, the reaction time is 1-24h, and the mass ratio of the carboxymethyl cellulose to the acyl chloride carbon black is 0.01-0.2: 1.
In a third aspect, the present invention provides the use of the easily dispersible carbon black conductive agent of the first aspect for a lithium ion battery.
Preferably, the easily-dispersible carbon black conductive agent is used for a high-power lithium ion battery, and the power value of the easily-dispersible carbon black conductive agent is greater than 3C.
Compared with the prior art, the invention has the following beneficial effects:
(1) in the easily-dispersible carbon black conductive agent, the carboxymethyl cellulose is grafted on the surface of carbon black, so that the easily-dispersible carbon black conductive agent has good solubility in water, and can prevent the carbon black from agglomerating to further form well-dispersed lithium ion battery slurry; compared with the traditional carbon black, the internal resistance of the high-power lithium battery prepared from the carbon black is obviously reduced, and the rate capability of the high-power lithium battery is also obviously improved; the capacity retention rate of a battery prepared by the easily-dispersible carbon black conductive agent can still reach over 90 percent under the discharge rate of 15C;
(2) the preparation method of the easily dispersible carbon black conductive agent can graft a large amount of carboxymethyl cellulose on the surface of carbon black, so that the requirement of the carbon black on dispersibility in the preparation process of lithium ion battery slurry is met, and the effects of reducing the internal resistance of a battery and improving the rate capability are achieved;
(3) the preparation method of the easily dispersible carbon black conductive agent is simple, easy to operate and suitable for industrial production.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The preparation method of the easily-dispersed carbon black conductive agent comprises the following steps:
(1) placing the beaker filled with 500ml of water in a water bath kettle at 50 ℃, adding 10g of water with the specific surface area of 95m2High-performance carbon black conductive agent with the average particle size of 30 nm/g is dispersed in advance for 2 hours by using ultrasonic waves, and then ozone is introduced at the speed of 50mL/min whileStirring and introducing ozone for reaction for 24 hours, filtering after the reaction is finished, and drying filter residues to obtain oxidized carbon black;
(2) adding oxalyl chloride into the oxidized carbon black in the step (1), carrying out reflux reaction in a water bath kettle at 50 ℃ for 24 hours, and removing an acyl chloride reagent to obtain acyl chloride carbon black;
(3) and (3) adding the acyl chlorination carbon black obtained in the step (2) into a DMF (dimethyl formamide) solution dissolved with 0.5g of carboxymethyl fiber (with the molecular weight of 5 ten thousand) in advance, carrying out reflux reaction for 12 hours, and leaching and drying for multiple times to obtain an easily dispersible carbon black product.
Example 2
This example is different from example 1 in that the specific surface area of the high-performance carbon black conductive agent used in step (1) is 275m2The average particle diameter was 20nm in terms of/g, and other parameters and conditions were exactly the same as those in example 1.
Example 3
This example is different from example 1 in that the molecular weight of carboxymethyl cellulose in step (3) is 9 ten thousand, and other parameters and conditions are identical to those in example 1.
Example 4
This example differs from example 1 in that ozone was replaced with oxygen in step (1) and other parameters and conditions were exactly the same as in example 1.
Comparative example 1
This comparative example directly used the specific surface area of 95m used in example 12A high-performance carbon black conductive agent having an average particle diameter of about 30nm per gram.
And (3) performance testing:
preparing a negative pole piece: the easily dispersible carbon black conductive agents of examples 1 to 4 were mixed with the negative electrode main material and the binder in the following proportions: conductive agent: CMC: mixing SBR (styrene butadiene rubber) at a ratio of 95:2:1.7:1.2 to prepare slurry, coating the slurry on a foil, and drying and rolling to prepare negative electrode pieces A1, A2, A3 and A4 respectively;
mixing the conductive agent, the negative main material and the binder in the comparative example 1 according to the same proportion to prepare slurry, coating the slurry on a foil, and drying and rolling to prepare a negative pole piece B;
testing the resistance values of the negative pole pieces A1, A2, A3, A4 and the negative pole piece B, wherein the test results are shown in Table 1;
TABLE 1
Pole piece resistance/m omega | |
Example 1 | 20 |
Example 2 | 45 |
Example 3 | 30 |
Example 4 | 21 |
Comparative example 1 | 50 |
As can be seen from Table 1, the negative electrode plate prepared by using the easily dispersible carbon black conductive agent has smaller resistance.
Preparing a battery: a cylindrical battery was assembled by winding a negative electrode sheet a1 (corresponding to the easily dispersible carbon black conductive agent in example 1), a separator, and a positive electrode sheet, which was a main material: conductive agent: PVDF (95.5: 3: 1.5), a base film with the thickness of 14 microns is adopted as a diaphragm, 1M lithium hexafluorophosphate electrolyte is adopted as the electrolyte, and the battery A is obtained after formation and aging;
winding and assembling a negative pole piece B, a diaphragm and a positive pole piece into a cylindrical battery, wherein the positive pole piece and the diaphragm are the same as those in the battery A, and the electrolyte adopts 1M lithium hexafluorophosphate electrolyte, and is subjected to formation and aging to obtain a battery B;
cycle capacity retention rate test: battery a and battery B were charged at 0.5C and discharged at 0.2C, 0.5C, 1C, 3C, 5C, 10C, 15C, respectively, with the test results shown in table 2;
TABLE 2
As can be seen from the above table 2, the battery prepared by using the easily dispersible carbon black conductive agent of the invention has excellent cycle performance, and is particularly suitable for high-power lithium ion batteries; the capacity retention rate of the battery prepared by the easily-dispersible carbon black conductive agent can still reach over 90 percent under the discharge rate of 15C.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. An easily dispersible carbon black conductive agent, characterized in that the easily dispersible carbon black conductive agent comprises carbon black and carboxymethyl cellulose grafted on the surface of the carbon black.
2. The easily dispersible carbon black conductive agent according to claim 1, wherein the carboxymethyl cellulose has a molecular weight of 3 to 8 ten thousand;
preferably, the specific surface area of the easily dispersible carbon black conductive agent is 90-130m2/g。
3. The easily dispersible carbon black conductive agent according to claim 1 or 2, wherein a raw material of the easily dispersible carbon black conductive agent comprises virgin carbon black;
preferably, the particle size of the primary carbon black is 10-30 nm;
preferably, the specific surface area of the raw carbon black is 60 to 300m2/g。
4. A method for preparing the easily dispersible carbon black conductive agent according to any one of claims 1 to 3, comprising the steps of:
(1) oxidizing the primary carbon black to obtain oxidized carbon black;
(2) introducing acyl chloride groups on the surface of the oxidized carbon black in the step (1) to obtain acyl chloride carbon black;
(3) and (3) reacting the acyl chloride carbon black in the step (2) with carboxymethyl cellulose to obtain the easily dispersible carbon black conductive agent.
5. The method according to claim 4, wherein the step (1) of oxidizing the virgin carbon black comprises dispersing the virgin carbon black in water, and introducing a gaseous oxidizing agent to conduct an oxidation reaction to obtain the oxidized carbon black.
6. The method of claim 5, wherein the gaseous oxidant comprises oxygen and/or ozone;
preferably, the introduction rate of the gas oxidant is 1-100 mL/min;
preferably, the time of the oxidation reaction is more than or equal to 24 hours;
preferably, the temperature of the oxidation reaction is 30-80 ℃;
preferably, the oxidation reaction is accompanied by ultrasound;
preferably, the oxidation reaction in step (1) is further followed by solid-liquid separation and drying.
7. The production method according to any one of claims 4 to 6, wherein the method for introducing acid chloride groups to the surface of the oxidized carbon black in the step (2) comprises mixing the oxidized carbon black with an acid chloride reagent to perform an acid chloride reaction;
preferably, the acid chlorination reagent comprises at least one of phosgene, oxalyl chloride, phosphorus oxychloride, or phosphorus pentachloride;
preferably, the temperature of the acyl chlorination reaction is 25-80 ℃, and the time is 24-48 h;
preferably, after the acyl chlorination reaction is finished, removing the acyl chlorination reagent to obtain the acyl chlorination carbon black.
8. The method according to any one of claims 4 to 7, wherein the method for reacting the carbon black acylate chloride with the carboxymethyl cellulose in the step (3) comprises mixing the carbon black acylate chloride, the carboxymethyl cellulose and a solvent, and carrying out a grafting reaction to obtain the easily dispersible carbon black conductive agent;
preferably, the solvent is selected from at least one of water, chloroform, DMAC or DMF;
preferably, the temperature of the grafting reaction is 25-80 ℃ and the time is 1-24 h;
preferably, the mass ratio of the carboxymethyl cellulose to the carbon black chloride in the step (3) is 0.01-0.2: 1.
9. The method of any one of claims 4 to 8, wherein the method comprises the steps of:
(1) dispersing the original carbon black in an aqueous solution by using an ultrasonic method, introducing oxygen and/or ozone, carrying out an oxidation reaction at a temperature of between 30 and 80 ℃ for more than 24 hours, filtering and drying to obtain oxidized carbon black, wherein the introduction rate of the oxygen and/or the ozone is 1 to 100 mL/min; ultrasonic is always needed in the oxidation reaction process;
(2) adding the carbon black oxide obtained in the step (1) into an acyl chlorination reagent, carrying out acyl chlorination reaction for 24-48h at 25-80 ℃, and removing the acyl chlorination reagent to obtain the carbon black oxide, wherein the acyl chlorination reagent is selected from at least one of phosgene, oxalyl chloride, phosphorus oxychloride or phosphorus pentachloride;
(3) and (3) reacting the acyl chloride carbon black in the step (2) with carboxymethyl cellulose in a solvent to obtain the easily dispersible carbon black conductive agent, wherein the solvent is at least one of water, chloroform, DMAC (dimethylacetamide) or DMF (dimethyl formamide), the reaction temperature is 25-80 ℃, the reaction time is 1-24h, and the mass ratio of the carboxymethyl cellulose to the acyl chloride carbon black is 0.01-0.2: 1.
10. Use of the readily dispersible carbon black conductive agent according to any one of claims 1 to 3 in a lithium ion battery;
preferably, the easily-dispersible carbon black conductive agent is used for a high-power lithium ion battery, and the power value of the easily-dispersible carbon black conductive agent is greater than 3C.
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11148027A (en) * | 1997-11-17 | 1999-06-02 | Tokai Carbon Co Ltd | Easily water-dispersible carbon black and its production |
CN104788685A (en) * | 2015-04-28 | 2015-07-22 | 中科院广州化学有限公司南雄材料生产基地 | Modified carbon black, and preparation method and application thereof |
CN107369835A (en) * | 2016-05-12 | 2017-11-21 | 华为技术有限公司 | A kind of lithium ion battery conductive adhesive and preparation method thereof, lithium ion battery electrode piece and preparation method and lithium ion battery |
CN109777159A (en) * | 2019-03-25 | 2019-05-21 | 广西师范大学 | A kind of preparation method of lithium ion cell positive conductive agent, conductive agent slurry |
CN109935837A (en) * | 2018-11-23 | 2019-06-25 | 万向一二三股份公司 | A kind of lithium ion battery carbon-coated aluminum foils |
-
2020
- 2020-12-07 CN CN202011431393.3A patent/CN112542590A/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11148027A (en) * | 1997-11-17 | 1999-06-02 | Tokai Carbon Co Ltd | Easily water-dispersible carbon black and its production |
CN104788685A (en) * | 2015-04-28 | 2015-07-22 | 中科院广州化学有限公司南雄材料生产基地 | Modified carbon black, and preparation method and application thereof |
CN107369835A (en) * | 2016-05-12 | 2017-11-21 | 华为技术有限公司 | A kind of lithium ion battery conductive adhesive and preparation method thereof, lithium ion battery electrode piece and preparation method and lithium ion battery |
CN109935837A (en) * | 2018-11-23 | 2019-06-25 | 万向一二三股份公司 | A kind of lithium ion battery carbon-coated aluminum foils |
CN109777159A (en) * | 2019-03-25 | 2019-05-21 | 广西师范大学 | A kind of preparation method of lithium ion cell positive conductive agent, conductive agent slurry |
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