CN112382794B - Preparation method of graphite cathode lithium ion battery - Google Patents

Preparation method of graphite cathode lithium ion battery Download PDF

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CN112382794B
CN112382794B CN202010767197.7A CN202010767197A CN112382794B CN 112382794 B CN112382794 B CN 112382794B CN 202010767197 A CN202010767197 A CN 202010767197A CN 112382794 B CN112382794 B CN 112382794B
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negative
lithium ion
ion battery
negative electrode
graphite
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CN112382794A (en
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杨亦双
陈阳
韩笑
李凡群
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Wanxiang A123 Systems Asia Co Ltd
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Wanxiang Group Corp
Wanxiang A123 Systems Asia Co Ltd
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Abstract

The invention discloses a preparation method of a graphite cathode lithium ion battery, which comprises the following steps: (1) preparation of negative active material: A) heating asphalt to 140-150 ℃, adding an ethylene-vinyl acetate copolymer, a cross-linking agent and a catalyst, stirring at constant temperature for reaction, and cooling to obtain modified asphalt; B) mixing the modified asphalt and the needle-shaped coke powder, adding the mixture into a coating reaction kettle, and performing coating reaction to obtain a coated product; C) carbonizing and cooling the coated product to obtain a negative active material; (2) preparing a negative plate: adding a negative electrode active material, a conductive agent, a binder and a thickening agent into a solvent, uniformly stirring to obtain negative electrode slurry, coating the negative electrode slurry on a copper foil, and drying to obtain a negative electrode sheet; (3) and (6) assembling the battery. According to the invention, the surface of the graphite negative electrode is coated with a certain amount of amorphous carbon, so that the interface between the electrolyte and the graphite is improved, the dynamic performance of lithium ions on the graphite surface is improved, a negative electrode plate with complete lithium intercalation is obtained, and the rate capability of the battery is improved.

Description

Preparation method of graphite cathode lithium ion battery
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a preparation method of a graphite cathode lithium ion battery.
Background
The energy density of lithium ion batteries depends to a large extent on the negative electrode material, and from the commercialization of lithium ion batteries to the present, the most mature and widely used negative electrode material is carbon material, and most of the negative electrode material is still graphite. For example, a chinese patent publication No. CN101106191 discloses a method for preparing a composite graphite negative electrode material and a lithium ion battery using the same, in which the method for preparing the composite graphite negative electrode material is as follows: firstly, synthesizing graphite into Graphite Intercalation Compounds (GICs), then coating the GICs with a soft carbon precursor, carrying out heat treatment in an oxygen-isolated atmosphere at 700-3000 ℃, and sieving to obtain the composite graphite cathode material. The lithium ion battery prepared by using the composite graphite cathode material has the advantages of low initial irreversible capacity, good high-current charge and discharge performance, high capacity, long cycle life and the like.
Although graphite has very considerable electrochemical performance when being used as a lithium battery cathode material, the graphite has poor stability of a layered structure and is easy to collapse after long-time charge and discharge cycles, so that the specific capacity is seriously reduced and the energy storage life is greatly shortened; along with the increase of the graphitization degree, the lithium embedding difficulty is increased, the multiplying power performance of the battery is poor, and the battery cannot be charged and discharged by large current, otherwise, the battery can be damaged.
Disclosure of Invention
The invention aims to overcome the defects that when graphite is used as a negative electrode material of a lithium ion battery in the prior art, the graphite laminated structure has poor stability and is easy to collapse after long-time charge-discharge circulation, so that the specific capacity is seriously reduced and the energy storage life is greatly shortened; and along with the improvement of graphitization degree, the difficulty of lithium intercalation is improved, and the multiplying power performance of the battery is poorer, the preparation method of the graphite cathode lithium ion battery is provided, and the dynamic performance of lithium ions on the graphite surface is improved by coating a certain amount of amorphous carbon on the surface of the artificial graphite cathode, so that a cathode plate with complete lithium intercalation is obtained, and the multiplying power performance of the battery is improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a graphite cathode lithium ion battery comprises the following steps:
(1) preparation of negative active material:
A) heating asphalt to 140-150 ℃, adding an ethylene-vinyl acetate copolymer, a cross-linking agent and a catalyst, stirring at a constant temperature for reacting for 2-3 hours, and cooling to obtain modified asphalt;
B) mixing the modified asphalt and the needle-shaped coke powder, adding the mixture into a coating reaction kettle, and performing coating reaction for 1-2 hours at the temperature of 300-400 ℃ to obtain a coated product;
C) carbonizing the coated product at 700-1000 ℃ in a nitrogen atmosphere for 2-3 h, and cooling to room temperature to obtain the negative active material;
(2) preparing a negative plate: adding a negative electrode active material, a conductive agent, a binder and a thickening agent into a solvent, uniformly stirring to obtain negative electrode slurry, coating the negative electrode slurry on a copper foil, and drying, rolling and slicing to obtain a negative electrode sheet;
(3) assembling the battery: and assembling the prepared negative plate and the positive plate together by adopting a diaphragm for liquid injection, and forming to obtain the graphite negative lithium ion battery.
When the negative electrode active material is prepared, the modified asphalt is used for coating the needle coke powder, so that the surface of the artificial graphite is coated with a layer of uniform amorphous carbon, the artificial graphite with high graphitization degree is prevented from being in direct contact with electrolyte, the graphite laminated structure is prevented from being damaged, and the negative electrode plate with uniform and complete lithium intercalation is obtained; meanwhile, the amorphous carbon can improve the dynamic performance of lithium ions on the surface of graphite, solve the lithium intercalation defect in the formation process, and reduce the direct current impedance of the battery, thereby improving the rate capability of the battery.
Meanwhile, when the negative active material is prepared, the ethylene-vinyl acetate copolymer is used for modifying the asphalt under the action of the cross-linking agent and the catalyst in the step A), so that the softening point of the asphalt is improved, the content of light components in the asphalt is reduced, the gas overflow in the carbonization process is reduced, a compact amorphous carbon layer can be formed on the surface of the graphite after carbonization, the formation of defects such as cracks, holes and the like is avoided, the contact between the graphite and the electrolyte is further reduced, and the irreversible capacity in the first charge-discharge process is reduced. The addition of the cross-linking agent can improve the stability of the modified asphalt through the cross-linking effect and avoid the phase separation of the modified asphalt.
Preferably, the adding amount of the ethylene-vinyl acetate copolymer, the cross-linking agent and the catalyst in the step A) is 2-4%, 0.8-1.2% and 2-3% of the mass of the asphalt respectively.
Preferably, the crosslinking agent in step A) is divinylbenzene and the catalyst is p-toluenesulfonic acid.
Preferably, the modified asphalt and the needle-shaped coke powder in the step B) respectively account for 0.6-2.0% and 98.0-99.4% of the total mass of the mixture after the modified asphalt and the needle-shaped coke powder are mixed.
Preferably, the space velocity in the carbonization in the step C) is 0.5-1 m/min. The space velocity during carbonization can change the pore channel structure of the amorphous carbon layer on the surface of the graphite and the amorphous degree of the carbon layer, and the space velocity is within the range of the invention, so that the carbon skeleton of the amorphous carbon layer can be more ordered while the pore channel is left, thereby improving the electrochemical performance of the amorphous carbon layer.
Preferably, the negative electrode slurry in the step (2) comprises 96-98 parts by weight of a negative electrode material, 0.5-1 part by weight of a conductive agent, 0-1 part by weight of a thickening agent, 1-2 parts by weight of a binder and 60-250 parts by weight of a solvent.
Preferably, the preparation method of the binder in the step (2) comprises the following steps:
a) adding lithium acrylate, acrylamide and acrylonitrile into a reaction container according to the mass ratio of (1-3) to (1-3), and then adding the mixture according to the molar ratio of (2-3): 5, reacting potassium persulfate and sodium bisulfite at the temperature of 90-100 ℃ for 4-6 h to obtain a lithium acrylate-acrylamide-acrylonitrile copolymer; wherein the total mass of the potassium persulfate and the sodium bisulfite is 3-3.5% of the total mass of the lithium acrylate, the acrylamide and the acrylonitrile;
b) mixing the lithium acrylate-acrylamide-acrylonitrile copolymer with chloroform, adding benzoyl peroxide, wherein the ratio of the polymer to the chloroform to the benzoyl peroxide is 1g (10-15 mL) to 0.03-0.05 g, introducing chlorine gas at 90-140 ℃ for reaction for 1-6 h, and removing the solvent to obtain a chlorinated polymer;
c) and dissolving the chlorinated polymer in a KOH/ethanol solution, wherein the concentration of the KOH/ethanol solution is 1.0-2.5 mol/L, the ratio of the polymer to the KOH/ethanol solution is 1g (10-15 mL), reacting at 60-90 ℃ for 30-60 min, and removing the solvent to obtain the binder.
In the preparation process of the binder, firstly, the lithium acrylate-acrylamide-acrylonitrile copolymer is prepared through the step a), and hydrophilic units-CH exist in the lithium acrylate-acrylamide-acrylonitrile copolymer at the same time2CH(COO-)-、-CH2CH(CONH2) -, and the lipophilic unit-CH2Ch (cn) -, since the surface of the negative active material is hydrophobic, the lipophilic unit in the binder has a comparable affinity with the negative active material, and can improve the dispersion of the negative active material in water to achieve good stability of the negative paste and can provide a binding force with the negative active material; meanwhile, the hydrophilic groups on the binder can form hydrogen bonds with the surface of the copper foil, so that the binder and the current collector have good binding power. In conclusion, the binder used in the invention can play a role in binding the negative plate and also can play a role in suspending in the negative slurry, so that the binder in the invention can reduce the proportion of the thickening agent and the binder in the negative slurry; in addition, because the binder is a straight-chain polymer, branched chain crosslinking cannot occur, and the polymer cannot be dissolved in water, the solution formed by dissolving the binder in water is easier to form a film on the surface of the negative electrode active material, the solution has a larger contact area with the negative electrode active material, more binding points are formed, the binding property of the solution is improved, the intertwined polymer chains additionally provide part of binding property, the use amount of the binder in the negative electrode slurry can be further reduced by enhancing the binding effect of the binder, the proportion of the negative electrode active material is improved, and the electrochemical performance of the battery is improved.
Meanwhile, the lithium acrylate-acrylamide-acrylonitrile copolymer is subjected to halogenation reaction and elimination reaction to form conjugated double bonds through the steps b) and c), and the formation of the conjugated double bonds can increase the electronic conductivity of the binder, so that the internal resistance of the battery is reduced, and the rate capability is improved; in addition, the increase of the electron conductivity of the binder can further reduce the amount of the conductive agent in the anode slurry, thereby increasing the proportion of the anode active material.
Preferably, the conductive agent in the step (2) is at least one of conductive carbon black, single-walled carbon nanotube and nano carbon fiber; the thickening agent is sodium carboxymethyl cellulose; the solvent is water.
Preferably, the positive electrode active material of the positive electrode plate in the step (3) is a nickel-cobalt-manganese ternary material.
Preferably, the separator in step (3) is a PP or PE based separator; the electrolyte during liquid injection is lithium hexafluorophosphate electrolyte.
Therefore, the invention has the following beneficial effects:
(1) when the negative electrode active material is prepared, the surface of the artificial graphite is coated with a layer of uniform amorphous carbon, so that the artificial graphite with high graphitization degree is prevented from being directly contacted with electrolyte, the damage of a graphite laminated structure is further avoided, and a negative electrode plate with uniform and complete lithium intercalation is obtained; meanwhile, the amorphous carbon can improve the dynamic performance of lithium ions on the surface of graphite, solve the lithium intercalation defect in the formation process and reduce the direct current impedance of the battery, thereby improving the rate capability of the battery;
(2) the ethylene-vinyl acetate copolymer is used for modifying the asphalt, so that the softening point of the asphalt is improved, and the content of light components in the asphalt is reduced, so that the overflow of gas in the carbonization process is reduced, a compact amorphous carbon layer can be formed on the surface of the graphite after carbonization, and the formation of defects such as cracks, holes and the like is avoided;
(3) the negative electrode binder adopts lithium acrylate-acrylamide-acrylonitrile copolymer which forms conjugated double bonds through halogenation reaction and elimination reaction, so that the binder can play a role in binding in a negative electrode sheet and playing a role in suspending in negative electrode slurry, the proportion of a thickening agent and the binder in the negative electrode slurry is reduced, the proportion of a negative electrode active substance is improved, the electronic conductivity of the binder can be increased, the internal resistance of a battery is reduced, and the electrochemical performance of the battery is improved.
Drawings
Fig. 1 is a picture of a negative electrode sheet after the cycle test of example 1.
Fig. 2 is a picture of the negative electrode sheet after the cycle test of comparative example 1.
Detailed Description
The invention is further described with reference to the following detailed description and accompanying drawings.
Example 1:
a preparation method of a graphite cathode lithium ion battery comprises the following steps:
(1) preparation of negative active material:
A) heating asphalt powder to 145 ℃, adding an ethylene-vinyl acetate copolymer accounting for 3% of the mass of the asphalt powder, 1% of divinylbenzene and 2.5% of p-toluenesulfonic acid, stirring at constant temperature for reaction for 2.5h, and cooling to obtain modified asphalt;
B) mixing modified asphalt and needle-shaped coke powder, adding the mixture into a coating reaction kettle, wherein the modified asphalt accounts for 1% of the total mass of the mixture, the needle-shaped coke powder accounts for 99% of the total mass of the mixture, and performing coating reaction at 350 ℃ for 1.5 hours to obtain a coated product;
C) carbonizing the coated product at 800 ℃ under nitrogen atmosphere at an airspeed of 0.8m/min for 2.5h, and cooling to room temperature to obtain a negative active material;
(2) preparing a negative plate: adding 97 parts by weight of negative active material, 0.8 part by weight of Super P, 1.5 parts by weight of binder and 0.5 part by weight of sodium carboxymethyl cellulose into deionized water, uniformly stirring to obtain negative slurry, coating the negative slurry on a copper foil, and drying, rolling and slicing to obtain a negative plate;
(3) assembling the battery: and assembling the prepared negative plate and a positive plate taking an NCM material as an active material together by using a PP-based diaphragm for injection, selecting lithium hexafluorophosphate as an electrolyte, and forming to obtain the graphite negative lithium ion battery.
The preparation method of the adhesive in the step (2) comprises the following steps:
a) adding lithium acrylate, acrylamide and acrylonitrile into a reaction vessel according to the mass ratio of 2:1:2, adding potassium persulfate and sodium bisulfite with the molar ratio of 1:2, and reacting at 95 ℃ for 5 hours to obtain a lithium acrylate-acrylamide-acrylonitrile copolymer; wherein the total mass of the potassium persulfate and the sodium bisulfite is 3.2 percent of the total mass of the lithium acrylate, the acrylamide and the acrylonitrile;
b) mixing the lithium acrylate-acrylamide-acrylonitrile copolymer with chloroform, adding benzoyl peroxide, wherein the ratio of the polymer to the chloroform to the benzoyl peroxide is 1g:12mL:0.04g, introducing chlorine gas at 110 ℃ for reaction for 4h, and removing the solvent to obtain a chlorinated polymer;
c) and dissolving the chlorinated polymer in a KOH/ethanol solution, wherein the concentration of the KOH/ethanol solution is 2mol/L, the ratio of the polymer to the KOH/ethanol solution is 1g:12mL, reacting at 75 ℃ for 40min, and removing the solvent to obtain the binder.
Example 2:
a preparation method of a graphite cathode lithium ion battery comprises the following steps:
(1) preparation of negative active material:
A) heating asphalt powder to 140 ℃, adding an ethylene-vinyl acetate copolymer accounting for 2% of the mass of the asphalt powder, 0.8% of divinylbenzene and 2% of p-toluenesulfonic acid, stirring at constant temperature for reaction for 2 hours, and cooling to obtain modified asphalt;
B) mixing modified asphalt and needle coke powder, adding the mixture into a coating reaction kettle, wherein the modified asphalt accounts for 0.6 percent of the total mass of the mixture, the needle coke powder accounts for 99.4 percent of the total mass of the mixture, and performing coating reaction at 300 ℃ for 2 hours to obtain a coated product;
C) carbonizing the coated product at 700 ℃ under nitrogen atmosphere at an airspeed of 0.5m/min for 3h, and cooling to room temperature to obtain a negative active material;
(2) preparing a negative plate: adding 96 parts by weight of negative active material, 0.5 part by weight of Super P and 2 parts by weight of binder into deionized water, uniformly stirring to obtain negative slurry, coating the negative slurry on copper foil, and drying, rolling and slicing to obtain a negative plate;
(3) assembling the battery: and assembling the prepared negative plate and a positive plate taking an NCM material as an active material together by using a PP-based diaphragm for injection, selecting lithium hexafluorophosphate as an electrolyte, and forming to obtain the graphite negative lithium ion battery.
The preparation method of the adhesive in the step (2) comprises the following steps:
a) adding lithium acrylate, acrylamide and acrylonitrile into a reaction vessel according to the mass ratio of 1:1:3, adding potassium persulfate and sodium bisulfite with the molar ratio of 2:5, and reacting at 90 ℃ for 6 hours to obtain a lithium acrylate-acrylamide-acrylonitrile copolymer; wherein the total mass of the potassium persulfate and the sodium bisulfite is 3 percent of the total mass of the lithium acrylate, the acrylamide and the acrylonitrile;
b) mixing the lithium acrylate-acrylamide-acrylonitrile copolymer with chloroform, adding benzoyl peroxide, wherein the ratio of the polymer to the chloroform to the benzoyl peroxide is 1g:10mL:0.03g, introducing chlorine gas at 90 ℃ for reacting for 6h, and removing the solvent to obtain a chlorinated polymer;
c) and dissolving the chlorinated polymer in a KOH/ethanol solution, wherein the concentration of the KOH/ethanol solution is 1mol/L, the ratio of the polymer to the KOH/ethanol solution is 1g:10mL, reacting at 60 ℃ for 60min, and removing the solvent to obtain the binder.
Example 3:
a preparation method of a graphite cathode lithium ion battery comprises the following steps:
(1) preparation of negative active material:
A) heating asphalt powder to 150 ℃, adding an ethylene-vinyl acetate copolymer accounting for 4% of the mass of the asphalt powder, 1.2% of divinylbenzene and 3% of p-toluenesulfonic acid, stirring at constant temperature for reaction for 3 hours, and cooling to obtain modified asphalt;
B) mixing modified asphalt and needle-shaped coke powder, adding the mixture into a coating reaction kettle, wherein the modified asphalt accounts for 2% of the total mass of the mixture, the needle-shaped coke powder accounts for 98% of the total mass of the mixture, and performing coating reaction at 400 ℃ for 1 hour to obtain a coated product;
C) carbonizing the coated product at 1000 ℃ under nitrogen atmosphere at an airspeed of 1m/min for 2h, and cooling to room temperature to obtain a negative active material;
(2) preparing a negative plate: adding 98 parts by weight of negative electrode active material, 1 part by weight of SWCNT, 1 part by weight of binder and 1 part by weight of sodium carboxymethylcellulose into deionized water, uniformly stirring to obtain negative electrode slurry, coating the negative electrode slurry on copper foil, and drying, rolling and slicing to obtain a negative electrode sheet;
(3) assembling the battery: and assembling the prepared negative plate and a positive plate taking an NCM material as an active material together by using a PE-based diaphragm for injection, selecting lithium hexafluorophosphate as an electrolyte, and forming to obtain the graphite negative lithium ion battery.
The preparation method of the adhesive in the step (2) comprises the following steps:
a) adding lithium acrylate, acrylamide and acrylonitrile into a reaction vessel according to the mass ratio of 3:1:1, adding potassium persulfate and sodium bisulfite with the molar ratio of 3:5, and reacting at 100 ℃ for 4 hours to obtain a lithium acrylate-acrylamide-acrylonitrile copolymer; wherein the total mass of the potassium persulfate and the sodium bisulfite is 3.5 percent of the total mass of the lithium acrylate, the acrylamide and the acrylonitrile;
b) mixing the lithium acrylate-acrylamide-acrylonitrile copolymer with chloroform, adding benzoyl peroxide, wherein the ratio of the polymer to the chloroform to the benzoyl peroxide is 1g:15mL:0.05g, introducing chlorine gas at 140 ℃ for reaction for 1h, and removing the solvent to obtain a chlorinated polymer;
c) and dissolving the chlorinated polymer in a KOH/ethanol solution, wherein the concentration of the KOH/ethanol solution is 2.5mol/L, the ratio of the polymer to the KOH/ethanol solution is 1g:15mL, reacting at 90 ℃ for 30min, and removing the solvent to obtain the binder.
Comparative example 1:
a preparation method of a graphite cathode lithium ion battery comprises the following steps:
(1) preparation of negative active material: needle-shaped coke powder is adopted as a negative active material;
(2) preparing a negative plate: adding 97 parts by weight of negative active material, 0.8 part by weight of Super P, 1.5 parts by weight of binder and 0.5 part by weight of sodium carboxymethyl cellulose into deionized water, uniformly stirring to obtain negative slurry, coating the negative slurry on a copper foil, and drying, rolling and slicing to obtain a negative plate;
(3) assembling the battery: and assembling the prepared negative plate and a positive plate taking an NCM material as an active material together by using a PP-based diaphragm for injection, selecting lithium hexafluorophosphate as an electrolyte, and forming to obtain the graphite negative lithium ion battery.
Wherein the binder in the step (2) is prepared by the same method as in example 1.
Comparative example 2:
a preparation method of a graphite cathode lithium ion battery comprises the following steps:
(1) preparation of negative active material:
A) mixing asphalt powder and needle coke powder, adding the mixture into a coating reaction kettle, wherein the asphalt powder accounts for 1% of the total mass of the mixture, the needle coke powder accounts for 99% of the total mass of the mixture, and performing coating reaction at 350 ℃ for 1.5 hours to obtain a coated product;
B) carbonizing the coated product at 800 ℃ under nitrogen atmosphere at an airspeed of 0.8m/min for 2.5h, and cooling to room temperature to obtain a negative active material;
(2) preparing a negative plate: adding 97 parts by weight of negative active material, 0.8 part by weight of Super P, 1.5 parts by weight of binder and 0.5 part by weight of sodium carboxymethyl cellulose into deionized water, uniformly stirring to obtain negative slurry, coating the negative slurry on a copper foil, and drying, rolling and slicing to obtain a negative plate;
(3) assembling the battery: and assembling the prepared negative plate and a positive plate taking an NCM material as an active material together by using a PP-based diaphragm for injection, selecting lithium hexafluorophosphate as an electrolyte, and forming to obtain the graphite negative lithium ion battery.
Wherein the binder in the step (2) is prepared by the same method as in example 1.
Comparative example 3:
a preparation method of a graphite cathode lithium ion battery comprises the following steps:
(1) preparation of negative active material:
A) heating asphalt powder to 145 ℃, adding an ethylene-vinyl acetate copolymer accounting for 3% of the mass of the asphalt powder, 1% of divinylbenzene and 2.5% of p-toluenesulfonic acid, stirring at constant temperature for reaction for 2.5h, and cooling to obtain modified asphalt;
B) mixing modified asphalt and needle-shaped coke powder, adding the mixture into a coating reaction kettle, wherein the modified asphalt accounts for 1% of the total mass of the mixture, the needle-shaped coke powder accounts for 99% of the total mass of the mixture, and performing coating reaction at 350 ℃ for 1.5 hours to obtain a coated product;
C) carbonizing the coated product at 800 ℃ under nitrogen atmosphere at an airspeed of 0.8m/min for 2.5h, and cooling to room temperature to obtain a negative active material;
(2) preparing a negative plate: adding 97 parts by weight of negative active material, 0.8 part by weight of Super P, 1.5 parts by weight of styrene butadiene rubber and 0.5 part by weight of sodium carboxymethyl cellulose into deionized water, uniformly stirring to obtain negative slurry, coating the negative slurry on a copper foil, and drying, rolling and slicing to obtain a negative plate;
(3) assembling the battery: and assembling the prepared negative plate and a positive plate taking an NCM material as an active material together by using a PP-based diaphragm for injection, selecting lithium hexafluorophosphate as an electrolyte, and forming to obtain the graphite negative lithium ion battery.
Comparative example 4:
a preparation method of a graphite cathode lithium ion battery comprises the following steps:
(1) preparation of negative active material:
A) heating asphalt powder to 145 ℃, adding an ethylene-vinyl acetate copolymer accounting for 3% of the mass of the asphalt powder, 1% of divinylbenzene and 2.5% of p-toluenesulfonic acid, stirring at constant temperature for reaction for 2.5h, and cooling to obtain modified asphalt;
B) mixing modified asphalt and needle-shaped coke powder, adding the mixture into a coating reaction kettle, wherein the modified asphalt accounts for 1% of the total mass of the mixture, the needle-shaped coke powder accounts for 99% of the total mass of the mixture, and performing coating reaction at 350 ℃ for 1.5 hours to obtain a coated product;
C) carbonizing the coated product at 800 ℃ under nitrogen atmosphere at an airspeed of 0.8m/min for 2.5h, and cooling to room temperature to obtain a negative active material;
(2) preparing a negative plate: adding 97 parts by weight of negative active material, 0.8 part by weight of Super P, 1.5 parts by weight of binder and 0.5 part by weight of sodium carboxymethyl cellulose into deionized water, uniformly stirring to obtain negative slurry, coating the negative slurry on a copper foil, and drying, rolling and slicing to obtain a negative plate;
(3) assembling the battery: and assembling the prepared negative plate and a positive plate taking an NCM material as an active material together by using a PP-based diaphragm for injection, selecting lithium hexafluorophosphate as an electrolyte, and forming to obtain the graphite negative lithium ion battery.
The preparation method of the adhesive in the step (2) comprises the following steps: adding lithium acrylate, acrylamide and acrylonitrile into a reaction vessel according to the mass ratio of 2:1:2, adding potassium persulfate and sodium bisulfite with the molar ratio of 1:2, and reacting at 95 ℃ for 5 hours to obtain the binder; wherein the total mass of the potassium persulfate and the sodium bisulfite is 3.2 percent of the total mass of the lithium acrylate, the acrylamide and the acrylonitrile.
The peel strength of the negative electrode sheets and the performance of the lithium ion batteries manufactured in example 1 and comparative example 1 were measured, and the results are shown in table 1.
Table 1: and testing the performance of the negative plate and the lithium ion battery.
Figure BDA0002615150060000081
As can be seen from table 1, the lithium ion batteries prepared by the method in embodiments 1 to 3 have high peel strength and high capacity of the negative electrode sheet, and good cyclic charge-discharge performance and rate capability of the batteries; in the comparative example 1, the graphite is not coated by using asphalt, so that the cyclic charge and discharge performance and the rate capability of the battery are obviously reduced compared with those in the example 1; in comparative example 2, the asphalt was not modified, and the performance of the battery was also reduced as compared with that in example 1; in comparative example 3, the binder of the present invention was not used, but the conventional styrene butadiene rubber was used as the binder, and the peel strength of the negative electrode sheet was significantly reduced, and the battery performance was decreased; in the preparation of the binder in comparative example 4, the lithium acrylate-acrylamide-acrylonitrile copolymer was not subjected to subsequent modification, and the battery performance was also reduced as compared with that in example 1; as can be seen from fig. 1 and 2, the cycled surface of the negative electrode sheet in example 1 was uniform and no black spots appeared, whereas the cycled surface of the negative electrode sheet in comparative example 1 had more noticeable black spots. The method provided by the invention is proved to be capable of effectively improving the cycle charge and discharge performance and the rate capability of the lithium ion battery.

Claims (9)

1. A preparation method of a graphite cathode lithium ion battery is characterized by comprising the following steps:
(1) preparation of negative active material:
A) heating asphalt to 140-150 ℃, adding an ethylene-vinyl acetate copolymer, a cross-linking agent and a catalyst, stirring at a constant temperature for reacting for 2-3 hours, and cooling to obtain modified asphalt;
B) mixing the modified asphalt and the needle-shaped coke powder, adding the mixture into a coating reaction kettle, and performing coating reaction for 1-2 hours at the temperature of 300-400 ℃ to obtain a coated product;
C) carbonizing the coated product at 700-1000 ℃ in a nitrogen atmosphere for 2-3 h, and cooling to room temperature to obtain the negative active material;
(2) preparing a negative plate: adding a negative electrode active material, a conductive agent, a binder and a thickening agent into a solvent, uniformly stirring to obtain negative electrode slurry, coating the negative electrode slurry on a copper foil, and drying, rolling and slicing to obtain a negative electrode sheet;
the preparation method of the adhesive comprises the following steps:
a) adding lithium acrylate, acrylamide and acrylonitrile into a reaction container according to the mass ratio of (1-3) to (1-3), and then adding the mixture according to the molar ratio of (2-3): 5, reacting potassium persulfate and sodium bisulfite at the temperature of 90-100 ℃ for 4-6 h to obtain a lithium acrylate-acrylamide-acrylonitrile copolymer; wherein the total mass of the potassium persulfate and the sodium bisulfite is 3-3.5% of the total mass of the lithium acrylate, the acrylamide and the acrylonitrile;
b) mixing the lithium acrylate-acrylamide-acrylonitrile copolymer with chloroform, adding benzoyl peroxide, wherein the ratio of the polymer to the chloroform to the benzoyl peroxide is 1g (10-15 mL) to 0.03-0.05 g, introducing chlorine gas at 90-140 ℃ for reaction for 1-6 h, and removing the solvent to obtain a chlorinated polymer;
c) dissolving a chlorinated polymer in a KOH/ethanol solution, wherein the concentration of the KOH/ethanol solution is 1.0-2.5 mol/L, the ratio of the polymer to the KOH/ethanol solution is 1g (10-15 mL), reacting at 60-90 ℃ for 30-60 min, and removing the solvent to obtain the binder;
(3) assembling the battery: and assembling the prepared negative plate and the positive plate together by adopting a diaphragm for liquid injection, and forming to obtain the graphite negative lithium ion battery.
2. The preparation method of the graphite cathode lithium ion battery as claimed in claim 1, wherein the addition amounts of the ethylene-vinyl acetate copolymer, the crosslinking agent and the catalyst in the step A) are respectively 2-4%, 0.8-1.2% and 2-3% of the mass of the asphalt.
3. The method for preparing the graphite cathode lithium ion battery as claimed in claim 1 or 2, wherein the cross-linking agent in the step A) is divinylbenzene, and the catalyst is p-toluenesulfonic acid.
4. The method for preparing a graphite cathode lithium ion battery according to claim 1, wherein the modified asphalt and the needle-shaped coke powder in the step B) respectively account for 0.6-2.0% and 98.0-99.4% of the total mass of the mixture after mixing the modified asphalt and the needle-shaped coke powder.
5. The preparation method of the graphite cathode lithium ion battery as claimed in claim 1, wherein the space velocity during carbonization in the step C) is 0.5-1 m/min.
6. The method for preparing a graphite cathode lithium ion battery according to claim 1, wherein the cathode slurry in the step (2) comprises 96-98 parts by weight of cathode material, 0.5-1 part by weight of conductive agent, 0-1 part by weight of thickening agent, 1-2 parts by weight of binder and 60-250 parts by weight of solvent.
7. The method for preparing a graphite cathode lithium ion battery according to claim 1, wherein the conductive agent in the step (2) is at least one of conductive carbon black, single-walled carbon nanotube and carbon nanofiber; the thickening agent is sodium carboxymethyl cellulose; the solvent is water.
8. The method for preparing a graphite cathode lithium ion battery according to claim 1, wherein the cathode active material of the cathode plate in the step (3) is a nickel-cobalt-manganese ternary material.
9. The method for preparing the graphite cathode lithium ion battery according to claim 1, wherein the separator in the step (3) is a PP or PE-based separator; the electrolyte during liquid injection is lithium hexafluorophosphate electrolyte.
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