CN109888264A - A kind of high-energy cathode of lithium battery slurry and preparation method thereof - Google Patents
A kind of high-energy cathode of lithium battery slurry and preparation method thereof Download PDFInfo
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- CN109888264A CN109888264A CN201910320537.9A CN201910320537A CN109888264A CN 109888264 A CN109888264 A CN 109888264A CN 201910320537 A CN201910320537 A CN 201910320537A CN 109888264 A CN109888264 A CN 109888264A
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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
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- Y02E60/10—Energy storage using batteries
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Abstract
The problem of the invention discloses a kind of high-energy cathode of lithium battery slurries, are related to lithium battery production technical field, poor mainly for solving existing negative electrode slurry viscosity, not uniform enough when smearing slurry, directly influence the performance of battery；Including following raw material: negative electrode active material, binder, defoaming agent, high polymer additive, helps dispersing additive, thickener, fire retardant, buffer, surplus for solvent at conductive agent, the invention also discloses the preparation methods of the high-energy cathode of lithium battery slurry, the high polymer additive that the present invention uses has ionic conductivity, the ionic conductivity of negative electrode material can be enhanced, charge transfer resistance is reduced, the high rate performance of lithium ion battery can be improved；The present invention is added by thickening agent combination, ensure that various components play one's part to the full, and thickener keeps the stability of molecular structure in long-time placement process, is stablized size performance, is not agglomerated, do not settle.
Description
Technical field
The present invention relates to lithium battery production technical field, specifically a kind of high-energy cathode of lithium battery slurry and its preparation side
Method.
Background technique
It by lithium metal or lithium alloy is negative electrode material, using the battery of non-aqueous electrolytic solution that " lithium battery ", which is a kind of,.
Lithium battery is broadly divided into two classes: lithium metal battery and lithium ion battery.Lithium ion battery is without containing metallic state
Lithium, and can charge.
The negative electrode slurry of lithium battery mainly includes active material, conductive agent, adhesive and other additives, adhesive conduct
A part of negative electrode slurry can make negative electrode active material being bonded together more evenly, be conducive to the cyclicity for improving battery
Can, while making slurry that there is viscosity and uniformly being smeared, but in the prior art due to adhesive in battery cathode slurry
It is unable to reach desired effect, stability is poor, causes the negative electrode slurry viscosity of production poor therefore not equal enough when smearing slurry
It is even, directly influence the performance of battery.
Summary of the invention
The purpose of the present invention is to provide a kind of high-energy cathode of lithium battery slurries and preparation method thereof, to solve above-mentioned ask
Topic.
To achieve the above object, the invention provides the following technical scheme:
A kind of high-energy cathode of lithium battery slurry, including below according to the raw material of weight percent: negative electrode active material 40-46%,
Conductive agent 0.2-0.6%, it binder 1-3%, defoaming agent 0.2-0.4%, high polymer additive 2-6%, helps dispersing additive 2-4%, increase
Thick dose of 0.6-1%, fire retardant 1-3%, buffer 5-10%, surplus are solvent.
Based on the above technical solution, the present invention also provides following optional technical solutions:
In a kind of optinal plan: including below according to the raw material of weight percent: negative electrode active material 41-45%, conductive agent
0.3-0.5%, binder 1.5-2.5%, defoaming agent 0.25-0.35%, high polymer additive 3-5%, dispersing additive 2.5- is helped
3.5%, thickener 0.7-0.9%, fire retardant 1.5-2.5%, buffer 6-9%, surplus are solvent.
In a kind of optinal plan: including below according to the raw material of weight percent: negative electrode active material 43%, conductive agent
0.4%, binder 2%, defoaming agent 0.3%, high polymer additive 4%, help dispersing additive 3%, be thickener 0.8%, fire retardant 2%, slow
Fliud flushing 8%, surplus are solvent.
In a kind of optinal plan: the negative electrode active material is natural graphite, in artificial graphite, carbonaceous mesophase spherules
It is one or more.
In a kind of optinal plan: the conductive agent is conductive carbon black, electrically conductive graphite, graphene, acetylene black, conductive fibre
One of dimension, carbon nanotube are a variety of.
In a kind of optinal plan: the binder be sodium alginate, the defoaming agent be ethylene carbonate EC, ethyl alcohol and
One of isopropanol.
In a kind of optinal plan: the high polymer additive is one of alkane, alkene, aromatic hydrocarbon, described to help point
Scattered additive includes that the mass ratio of Tween 80 and sorbester p18, wherein Tween 80 and sorbester p18 is (0.8-1.6): 1.
In a kind of optinal plan: the thickener is butadiene-styrene rubber, polyacrylic acid, carboxymethyl cellulose, carboxymethyl fibre
It ties up plain sodium and chitin is mixed according to mass ratio for 1:1:2:2:1, the fire retardant is triphenyl phosphate and tetrabromophthalic anhydride,
Triphenyl phosphate and the mass ratio of tetrabromophthalic anhydride are 3:1.
In a kind of optinal plan: the buffer is buffered by acetic acid-sodium acetate buffer solution, citric acid-sodium hydroxide
Solution, sodium dihydrogen phosphate-sodium hydroxide buffer solution are 1:2:1 mixing according to mass ratio, and the solvent is deionized water.
In a kind of optinal plan: the preparation method of the high-energy cathode of lithium battery slurry, steps are as follows:
1) each raw material is weighed according to the ratio；
2) high mediate in planetary mixer in advance is added in negative electrode active material, conductive agent, binder, high polymer additive according to quantity
Mixed, mixing speed is revolution 6-10r/min, and mixing time is 10-45 minutes, obtains mixture A；
3) solvent is divided into three parts, a solvent is taken to be put into agitator tank together with thickener, stir 10-30min, with obtained
To thickener soln；
4) a solvent and defoaming agent are taken, dispersing additive is helped to mix, adjustment blender speed of agitator is 600-700r/min, even
Continuous stirring 120-180min, makes defoaming agent, dispersing additive is helped sufficiently to dissolve dispersion, obtain mixture B；
5) remaining a solvent is mixed with the mixture A of half, buffer is then heated to 45-60 DEG C simultaneously
Mixing is added, adjustment revolution revolving speed is 20-30r/min, and rotation revolving speed is 1800-2000r/min, 60-90min is continuously stirred,
Obtain mixture C；
6) thickener soln, remaining mixture A, mixture B and mixture C are mixed, continuously stirs 180-200min, it is stirred
Slurry is handled using ultrasonic wave in journey, the uniformity of slurry mixing is improved, to obtain required negative electrode slurry.
Compared to the prior art, beneficial effects of the present invention are as follows:
1, solid powder is improved molten as helping dispersing additive to dissolve in solvent using the mixture of Tween 80 and sorbester p18
Dispersion performance in agent；
2, the high polymer additive used has ionic conductivity, and the ionic conductivity of negative electrode material can be enhanced, and reduces charge
The high rate performance of lithium ion battery can be improved in transfer resistance；And there is certain flexibility, in negative electrode active material surface shape
At one layer of protection clad, the bulk effect that negative electrode active material occurs in charge and discharge process can be alleviated, improve lithium ion
The cycle performance of battery；
3, the present invention is added by thickening agent combination, ensure that various components play one's part to the full, and thickener is placed in long-time
The stability for keeping molecular structure in the process, stablizes size performance, does not agglomerate, do not settle；By the dosage after thickening agent combination
It substantially reduces, while guaranteeing Stability of Slurry, also improves negative electrode active material content, ensure that the base of lithium ion battery
This performance simultaneously, reduces the dosage of thickener, improves the volume and capacity ratio of lithium ion battery.
Specific embodiment
Following embodiment can be described in detail the present invention, and each embodiment cited by the present invention is only to illustrate the present invention,
It is not used to limit the scope of the present invention.Any modification apparent easy to know or change made for the present invention are without departure from the present invention
Spirit and scope.
Embodiment 1
In the embodiment of the present invention, a kind of high-energy cathode of lithium battery slurry, including below according to the raw material of weight percent: cathode
Active material 40%, binder 1%, defoaming agent 0.2%, high polymer additive 2%, helps dispersing additive 2%, thickening at conductive agent 0.2%
Agent 0.6%, fire retardant 1%, buffer 5%, surplus are solvent.
Wherein, the negative electrode active material is natural graphite, artificial graphite, carbonaceous mesophase spherules are 1:2:1 in mass ratio
It constitutes.
The conductive agent is conductive carbon black, electrically conductive graphite, graphene, acetylene black, conductive fiber, carbon nanotube according to quality
Than being constituted for 1:1:1:1:1:1.
The binder is sodium alginate, and the defoaming agent is ethylene carbonate EC.
The high polymer additive is alkane, and described to help dispersing additive include Tween 80 and sorbester p18, wherein Tween 80
Mass ratio with sorbester p18 is 0.8:1.
The thickener be butadiene-styrene rubber, polyacrylic acid, carboxymethyl cellulose, sodium carboxymethylcellulose and chitin according to
Mass ratio mixes for 1:1:2:2:1, and the fire retardant is triphenyl phosphate and tetrabromophthalic anhydride, triphenyl phosphate and tetrabromo-benzene
The mass ratio of acid anhydride is 3:1.
The buffer is by acetic acid-sodium acetate buffer solution, citric acid-sodium hydroxide buffer solution, sodium dihydrogen phosphate-hydrogen
Sodium oxide molybdena buffer solution is 1:2:1 mixing according to mass ratio, and the solvent is deionized water.
In the present embodiment, the preparation method of the high-energy cathode of lithium battery slurry, steps are as follows:
1) each raw material is weighed according to the ratio；
2) high mediate in planetary mixer in advance is added in negative electrode active material, conductive agent, binder, high polymer additive according to quantity
Mixed, mixing speed is revolution 6r/min, and mixing time is 10 minutes, obtains mixture A；
3) solvent is divided into three parts, a solvent is taken to be put into agitator tank together with thickener, stir 10min, preparation obtains
Thickener soln；
4) a solvent and defoaming agent are taken, dispersing additive is helped to mix, adjustment blender speed of agitator is 600r/min, is continuously stirred
120min is mixed, makes defoaming agent, dispersing additive is helped sufficiently to dissolve dispersion, obtain mixture B；
5) remaining a solvent is mixed with the mixture A of half, buffer is then heated to 45 DEG C and is added
Enter mixing, adjustment revolution revolving speed is 20r/min, and rotation revolving speed is 1800r/min, continuously stirs 60min, obtains mixture C；
6) thickener soln, remaining mixture A, mixture B and mixture C are mixed, continuously stirs 180min, in whipping process
Slurry is handled using ultrasonic wave, the uniformity of slurry mixing is improved, to obtain required negative electrode slurry.
Embodiment 2
In the embodiment of the present invention, a kind of high-energy cathode of lithium battery slurry, including below according to the raw material of weight percent: cathode
Active material 43%, binder 2%, defoaming agent 0.3%, high polymer additive 4%, helps dispersing additive 3%, thickening at conductive agent 0.4%
Agent 0.8%, fire retardant 2%, buffer 8%, surplus are solvent.
Wherein, the negative electrode active material is natural graphite.
The conductive agent be conductive carbon black, electrically conductive graphite, graphene according to mass ratio be 1:1:2 composition.
The binder is sodium alginate, and the defoaming agent is ethyl alcohol.
The high polymer additive is one of alkane, alkene, aromatic hydrocarbon, and described to help dispersing additive include Tween 80
With sorbester p18, wherein the mass ratio of Tween 80 and sorbester p18 is 1.2:1.
The thickener be butadiene-styrene rubber, polyacrylic acid, carboxymethyl cellulose, sodium carboxymethylcellulose and chitin according to
Mass ratio mixes for 1:1:2:2:1, and the fire retardant is triphenyl phosphate and tetrabromophthalic anhydride, triphenyl phosphate and tetrabromo-benzene
The mass ratio of acid anhydride is 3:1.
The buffer is by acetic acid-sodium acetate buffer solution, citric acid-sodium hydroxide buffer solution, sodium dihydrogen phosphate-hydrogen
Sodium oxide molybdena buffer solution is 1:2:1 mixing according to mass ratio, and the solvent is deionized water.
In the present embodiment, the preparation method of the high-energy cathode of lithium battery slurry, steps are as follows:
1) each raw material is weighed according to the ratio；
2) high mediate in planetary mixer in advance is added in negative electrode active material, conductive agent, binder, high polymer additive according to quantity
Mixed, mixing speed is revolution 8r/min, and mixing time is 30 minutes, obtains mixture A；
3) solvent is divided into three parts, a solvent is taken to be put into agitator tank together with thickener, stir 20min, preparation obtains
Thickener soln；
4) a solvent and defoaming agent are taken, dispersing additive is helped to mix, adjustment blender speed of agitator is 650r/min, is continuously stirred
150min is mixed, makes defoaming agent, dispersing additive is helped sufficiently to dissolve dispersion, obtain mixture B；
5) remaining a solvent is mixed with the mixture A of half, buffer is then heated to 55 DEG C and is added
Enter mixing, adjustment revolution revolving speed is 25r/min, and rotation revolving speed is 1900r/min, continuously stirs 75min, obtains mixture C；
6) thickener soln, remaining mixture A, mixture B and mixture C are mixed, continuously stirs 190min, in whipping process
Slurry is handled using ultrasonic wave, the uniformity of slurry mixing is improved, to obtain required negative electrode slurry.
Embodiment 3
In the embodiment of the present invention, a kind of high-energy cathode of lithium battery slurry, including below according to the raw material of weight percent: cathode
Active material 46%, binder 3%, defoaming agent 0.4%, high polymer additive 6%, helps dispersing additive 4%, thickening at conductive agent 0.6%
Agent 1%, fire retardant 3%, buffer 10%, surplus are solvent.
Wherein, the negative electrode active material is carbonaceous mesophase spherules.
The conductive agent be acetylene black, conductive fiber, carbon nanotube according to mass ratio be 1:1:1 composition.
The binder is sodium alginate, and the defoaming agent is isopropanol.
The high polymer additive is one of alkane, alkene, aromatic hydrocarbon, and described to help dispersing additive include Tween 80
With sorbester p18, wherein the mass ratio of Tween 80 and sorbester p18 is 1.6:1.
The thickener be butadiene-styrene rubber, polyacrylic acid, carboxymethyl cellulose, sodium carboxymethylcellulose and chitin according to
Mass ratio mixes for 1:1:2:2:1, and the fire retardant is triphenyl phosphate and tetrabromophthalic anhydride, triphenyl phosphate and tetrabromo-benzene
The mass ratio of acid anhydride is 3:1.
The buffer is by acetic acid-sodium acetate buffer solution, citric acid-sodium hydroxide buffer solution, sodium dihydrogen phosphate-hydrogen
Sodium oxide molybdena buffer solution is 1:2:1 mixing according to mass ratio, and the solvent is deionized water.
In the present embodiment, the preparation method of the high-energy cathode of lithium battery slurry, steps are as follows:
1) each raw material is weighed according to the ratio；
2) high mediate in planetary mixer in advance is added in negative electrode active material, conductive agent, binder, high polymer additive according to quantity
Mixed, mixing speed is revolution 10r/min, and mixing time is 45 minutes, obtains mixture A；
3) solvent is divided into three parts, a solvent is taken to be put into agitator tank together with thickener, stir 30min, preparation obtains
Thickener soln；
4) a solvent and defoaming agent are taken, dispersing additive is helped to mix, adjustment blender speed of agitator is 700r/min, is continuously stirred
180min is mixed, makes defoaming agent, dispersing additive is helped sufficiently to dissolve dispersion, obtain mixture B；
5) remaining a solvent is mixed with the mixture A of half, buffer is then heated to 60 DEG C and is added
Enter mixing, adjustment revolution revolving speed is 30r/min, and rotation revolving speed is 2000r/min, continuously stirs 90min, obtains mixture C；
6) thickener soln, remaining mixture A, mixture B and mixture C are mixed, continuously stirs 200min, in whipping process
Slurry is handled using ultrasonic wave, the uniformity of slurry mixing is improved, to obtain required negative electrode slurry.
The present invention, as helping dispersing additive to dissolve in solvent, improves solid-state using the mixture of Tween 80 and sorbester p18
The dispersion performance of powder in a solvent；The high polymer additive of use have ionic conductivity, can be enhanced negative electrode material from
Subconductivity reduces charge transfer resistance, the high rate performance of lithium ion battery can be improved；And there is certain flexibility,
Negative electrode active material surface forms one layer of protection clad, can alleviate the body that negative electrode active material occurs in charge and discharge process
Product effect, improves the cycle performance of lithium ion battery；The present invention is added by thickening agent combination, ensure that various components are sufficiently sent out
The effect of waving, thickener keep the stability of molecular structure in long-time placement process, stablize size performance, do not agglomerate, no
Sedimentation；Dosage after thickening agent combination is substantially reduced, while guaranteeing Stability of Slurry, also improves negative electrode active material
Content, the basic performance that ensure that lithium ion battery simultaneously, reduce the dosage of thickener, improve the volume ratio of lithium ion battery
Capacity.
The above, the only specific embodiment of the disclosure, but the protection scope of the disclosure is not limited thereto, it is any
Those familiar with the art can easily think of the change or the replacement in the technical scope that the disclosure discloses, and should all contain
It covers within the protection scope of the disclosure.Therefore, the protection scope of the disclosure should be subject to the protection scope in claims.
Claims (9)
1. a kind of high-energy cathode of lithium battery slurry, which is characterized in that including below according to the raw material of weight percent: cathode is living
Property substance 40-46%, conductive agent 0.2-0.6%, binder 1-3%, defoaming agent 0.2-0.4%, high polymer additive 2-6%, dispersion is helped
Additive 2-4%, thickener 0.6-1%, fire retardant 1-3%, buffer 5-10%, surplus are solvent.
2. high-energy cathode of lithium battery slurry according to claim 1, which is characterized in that including below according to weight percent
The raw material of ratio: negative electrode active material 43%, binder 2%, defoaming agent 0.3%, high polymer additive 4%, helps dispersion at conductive agent 0.4%
Additive 3%, thickener 0.8%, fire retardant 2%, buffer 8%, surplus are solvent.
3. high-energy cathode of lithium battery slurry according to claim 2, which is characterized in that the negative electrode active material is day
One of right graphite, artificial graphite, carbonaceous mesophase spherules are a variety of.
4. high-energy cathode of lithium battery slurry according to claim 2, which is characterized in that the conductive agent is conductive carbon
One of black, electrically conductive graphite, graphene, acetylene black, conductive fiber, carbon nanotube are a variety of.
5. high-energy cathode of lithium battery slurry according to claim 2, which is characterized in that the binder is alginic acid
Sodium, the defoaming agent are one of ethylene carbonate EC, ethyl alcohol and isopropanol.
6. high-energy cathode of lithium battery slurry according to claim 1, which is characterized in that the high polymer additive is alkane
One of hydrocarbon, alkene, aromatic hydrocarbon, described to help dispersing additive include Tween 80 and sorbester p18, wherein Tween 80 and sorbester p18
Mass ratio be (0.8-1.6): 1.
7. high-energy cathode of lithium battery slurry according to claim 1, which is characterized in that the thickener is butylbenzene rubber
Glue, polyacrylic acid, carboxymethyl cellulose, sodium carboxymethylcellulose and chitin are mixed according to mass ratio for 1:1:2:2:1,
The fire retardant is triphenyl phosphate and tetrabromophthalic anhydride, and the mass ratio of triphenyl phosphate and tetrabromophthalic anhydride is 3:1.
8. high-energy cathode of lithium battery slurry according to claim 1, which is characterized in that the buffer is by acetic acid-second
Sour sodium buffer solution, citric acid-sodium hydroxide buffer solution, sodium dihydrogen phosphate-sodium hydroxide buffer solution are according to mass ratio
1:2:1 mixing, the solvent are deionized water.
9. the preparation method of -8 any high-energy cathode of lithium battery slurries according to claim 1, which is characterized in that step
It is as follows:
1) each raw material is weighed according to the ratio；
2) high mediate in planetary mixer in advance is added in negative electrode active material, conductive agent, binder, high polymer additive according to quantity
Mixed, mixing speed is revolution 6-10r/min, and mixing time is 10-45 minutes, obtains mixture A；
3) solvent is divided into three parts, a solvent is taken to be put into agitator tank together with thickener, stir 10-30min, with obtained
To thickener soln；
4) a solvent and defoaming agent are taken, dispersing additive is helped to mix, adjustment blender speed of agitator is 600-700r/min, even
Continuous stirring 120-180min, makes defoaming agent, dispersing additive is helped sufficiently to dissolve dispersion, obtain mixture B；
5) remaining a solvent is mixed with the mixture A of half, buffer is then heated to 45-60 DEG C simultaneously
Mixing is added, adjustment revolution revolving speed is 20-30r/min, and rotation revolving speed is 1800-2000r/min, 60-90min is continuously stirred,
Obtain mixture C；
6) thickener soln, remaining mixture A, mixture B and mixture C are mixed, continuously stirs 180-200min, it is stirred
Slurry is handled using ultrasonic wave in journey, the uniformity of slurry mixing is improved, to obtain required negative electrode slurry.
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| CN110190258A (en) * | 2019-06-06 | 2019-08-30 | 上海电气集团股份有限公司 | Aqueous composite mortar of Si-C composite material and preparation method thereof, lithium ion battery |
| CN110311109A (en) * | 2019-06-28 | 2019-10-08 | 徐州硕祥信息科技有限公司 | A kind of preparation method based on copper oxide composite lithium ion battery negative electrode material |
| CN112397695A (en) * | 2020-11-13 | 2021-02-23 | 河北零点新能源科技有限公司 | Hybrid process for improving quick charging performance of lithium battery |
| WO2021254157A1 (en) * | 2020-06-17 | 2021-12-23 | Guangdong Haozhi Technology Co., Limited | Slurry composition for flexible electrode in secondary battery |
| CN114614007A (en) * | 2022-02-17 | 2022-06-10 | 东莞凯德新能源有限公司 | Lithium ion battery anode slurry and preparation method thereof |
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