CN102738446A - Lithium ion battery slurry, preparation method of the lithium ion battery slurry, and lithium ion battery - Google Patents

Lithium ion battery slurry, preparation method of the lithium ion battery slurry, and lithium ion battery Download PDF

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Publication number
CN102738446A
CN102738446A CN2011100958394A CN201110095839A CN102738446A CN 102738446 A CN102738446 A CN 102738446A CN 2011100958394 A CN2011100958394 A CN 2011100958394A CN 201110095839 A CN201110095839 A CN 201110095839A CN 102738446 A CN102738446 A CN 102738446A
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lithium ion
ion battery
preparation
pulp
powder
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CN102738446B (en
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马忠龙
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Shenzhen Bak Power Battery Co Ltd
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Shenzhen Bak Battery Co Ltd
Bak International Tianjin Ltd
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/10Energy storage using batteries

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Abstract

The invention discloses a preparation method of lithium ion battery slurry. The preparation method comprises the following steps of 1, preparing a glue solution having a concentration of 3 to 7% by an adhesive, 2, putting one or more active substances and one or more conducting additives into a three-arm planetary stirrer, and uniformly mixing the mixture into powder at a low speed, 3, adding 1 to 15% of a solvent into the powder obtained by the step 2, and uniformly mixing the mixture into wet powder at a low speed, wherein a ratio of the total mass of the solvent to the mass of the powder is in a range of (55: 4) to (50: 50), 4, adding 20 to 50% of the glue solution and the rest of the solvent into the wet powder, and uniformly mixing at a high speed, and 5, adding the rest of the glue solution into the mixture obtained by the step 4, uniformly stirring at a low speed for 5 to 10 minutes, and then stirring at a high speed for 2 to 5 hours to obtain the lithium ion battery slurry. The invention also discloses the lithium ion battery slurry and a battery pole piece prepared by the preparation method, and a lithium ion battery.

Description

Pulp of lithium ion battery and preparation method thereof, and lithium ion battery
[technical field]
The present invention relates to the lithium ion battery field, especially relate to a kind of preparation method of pulp of lithium ion battery, use the pulp of lithium ion battery of this method preparation, and use the battery pole piece and the lithium ion battery of this pulp of lithium ion battery.
[background technology]
In the manufacture process of lithium ion battery, batch mixing is a crucial step, and the quality of batch mixing gained slurry will directly influence each item performance of finished product battery.Traditional method for mixing has two kinds, and a kind of is that active material and binding agent, solvent, conductive agent etc. are stirred according to certain stir speed (S.S.) in mixer after well according to certain mixed, is modulated into required slurry; A kind of in addition method for mixing is in the process of batch mixing, active material and binding agent, solvent, conductive agent etc. to be added stirring in batches according to certain ratio, is modulated into required slurry.
Yet; In the whipping process of above-mentioned two kinds of methods; Powder such as active material and conductive agent is easy to form " ash bag " and is dispersed in the slurry; Cause the mixing of slurry inhomogeneous, make the electrode plates dressing after the slurry inhomogeneous, on the electrode plates after the slurry, have local " convexity " and bubble " spot ".Local " convexity " will cause battery in charge and discharge process, to have the preferential reaction point, and be serious even can diaphragm cause battery short circuit, becomes the potential safety hazard of battery; Bubble " spot " then can make the utilance of active material descend, and has influenced the capacity of battery.
[summary of the invention]
Based on this, be necessary to provide a kind of preparation method who improves the inhomogeneity pulp of lithium ion battery of distribution of particles in the pulp of lithium ion battery.
A kind of preparation method of pulp of lithium ion battery comprises the steps:
Step 1, to use bonding agent to prepare concentration be 3%~7% glue;
Step 2, with active material and conductive agent in three arm planetary mixers, under low speed, be uniformly mixed to form powder;
Add in step 3, the powder in step 2 solvent total amount 1%~15%, under low speed, be uniformly mixed to form wet powder, wherein, the total amount of solvent and the mass ratio of said powder are 55: 4~50: 50;
20%~50% and the remaining solvent that add glue in step 4, the wet powder in step 3 evenly mix under at a high speed; And
Step 5, add remaining glue, under low speed, evenly stirred 5~10 minutes earlier, then at stirring 2~5 hours down at a high speed, formation pulp of lithium ion battery.
In a preferred embodiment, said binding agent is a kind of or its mixture in butadiene-styrene rubber, sodium carboxymethylcellulose, Kynoar, polyacrylate, the polyurethane.
In a preferred embodiment, said active material is LiCoO 2, LiMn 2O 4, LiNiO 2, lithium-nickel-cobalt-oxygen, lithium nickel cobalt manganese oxygen, lithium nickel cobalt alumina, LiFePO 4, a kind of or its mixture in graphite, lithium titanate, hard carbon, silicon and the silicon alloy, said conductive agent is a kind of and composition thereof in carbon black, carbon fiber, CNT and the graphite.
In a preferred embodiment, said solvent is water or N-methyl pyrrolidone.
In a preferred embodiment, in the step 2, the time of mixing is 10~30 minutes; In the step 3, the time of mixing is 40~100 minutes.
In a preferred embodiment, step 4 and step 5 are carried out under 40~70 ℃.
In a preferred embodiment, said low speed is 5~8rpm; Said high speed is 22~24rpm.
In addition, also be necessary to provide a kind of pulp of lithium ion battery of processing by above-mentioned preparation method.
In addition, also be necessary to provide a kind of battery pole piece of processing by above-mentioned pulp of lithium ion battery.
In addition, also be necessary to provide a kind of lithium ion battery that contains above-mentioned battery pole piece.
Said method is taked unique mixing method; Can be implemented in the equipment and can accomplish whole batch mixing process, the pulp of lithium ion battery of preparation has good uniformity, and; Since better controlled reunion and the size of agglomerated particle of particle; The structure that is difficult to disperse of effectively having avoided conductive agent and rubber powder to form makes that the cell size granularity of preparation is little, good stability, viscosity change for a short time, places not sedimentation for a long time.
[description of drawings]
Through the more specifically explanation of the preferred embodiments of the present invention shown in the accompanying drawing, above-mentioned and other purpose, characteristic and advantage of the present invention will be more clear.
Fig. 1 is preparation method's the flow chart of the pulp of lithium ion battery of an execution mode.
[embodiment]
For make above-mentioned purpose of the present invention, feature and advantage can be more obviously understandable, does detailed explanation below in conjunction with the accompanying drawing specific embodiments of the invention.A lot of details have been set forth in the following description so that make much of the present invention.But the present invention can implement much to be different from alternate manner described here, and those skilled in the art can do similar improvement under the situation of intension of the present invention, so the present invention does not receive the restriction of following disclosed practical implementation.
The preparation method of the pulp of lithium ion battery of one execution mode comprises the steps.
Step S101, to use bonding agent to prepare concentration be 3%~7% glue.
Can bonding agent be dissolved in the solvent, the formation mass concentration is 3%~7% glue.Wherein, binding agent is preferably a kind of or its mixture in butadiene-styrene rubber (SBR), sodium carboxymethylcellulose (CMC), Kynoar (PVDF), polyacrylate, the polyurethane.Solvent can be common solvent, is preferably water or N-methyl pyrrolidone (NMP).The concentration of above-mentioned glue can not be De Taigao, and preferably in 3%~7% scope, the glue of this concentration is easy to prepare, and can in follow-up adding powder, can reduce the formation of micelle.
Step S102, with active material and conductive agent in three arm planetary mixers, under low speed, be uniformly mixed to form powder.
Said active material comprises anode active material and cathode active material.Anode active material comprises LiCoO 2, LiMn 2O 4, LiNiO 2, lithium-nickel-cobalt-oxygen, lithium nickel cobalt manganese oxygen, lithium nickel cobalt alumina and LiFePO 4In at least a.Cathode active material comprises at least a in graphite, lithium titanate, hard carbon, silicon and the silicon alloy.
Conductive agent comprises a kind of and composition thereof in carbon black, carbon fiber, CNT and the graphite.
The additional proportion of active material and conductive agent can be confirmed through conventional method, not limit at this.
The viscoid that three arm planetary mixers blend together solid (powder body) and liquid, particularly to the stirring of plastic flow kinetoplast material, mixing has premium properties, the most variety production of suitable vertical kneading.Through heating, vacuum decompression can make water-soluble type and solvent-borne type material increase gloss and convergence powdery.The mixing part is made up of three frame type paddles, through special planetary motion, plays powerful mixing, stirring action.
Three arm planetary mixers generally have two kinds of operating states of low speed and high speed when using.Wherein low speed is 5~8rpm; Be 22~24rpm at a high speed.The time of mixing among the step S102 is preferably 10~30 minutes.
Add in step S103, the powder in step S102 solvent total amount 1%~15%, under low speed, be uniformly mixed to form wet powder, wherein, the total amount of solvent and the mass ratio of said powder are 55: 4~50: 50.
Solvent can be common solvent, is preferably water or N-methyl pyrrolidone (NMP).
Mixed powder can make that powder surface is wetting after adding little solvent, the moistened surface powder, and surface tension is improved, and has reduced the possibility of particle agglomeration.
20%~50% and the remaining solvent that add glue in step S104, the wet powder in step S103 evenly mix under at a high speed.
Said process is called as dilution for the first time.The viscosity that quantity of solvent that dilution for the first time adds and glue amount will guarantee slurry can not be too high, and the slurry of formation is shear shinning shape fluid, can not is to shear retrogradation shape fluid.So when remaining solvent was added, the amount of regulating the adding glue was between the 20%-50% of total amount.The addition of above-mentioned glue is to confirm according to final solid content and the powder surface character that forms of slurry.
Preferably, in the process of dilution for the first time, the temperature that keeps slurry to help the dispersion and the disintegration of the micelle in the slurries, makes slurry more even at 40~70 ℃.The thermostatted water that for example can in the chuck of the agitator of three arm planetary mixers, feed 40~70 ℃ drives trip temperature control into.
Step S105, add remaining glue, under low speed, evenly stirred 5~10 minutes earlier, then at stirring 2~5 hours down at a high speed, formation pulp of lithium ion battery.
Said process is called as dilution for the second time.Dilution for the second time is will add all residue glues to carry out the stirring of maximum speed, and powder and glue are farthest disperseed, and forms final pulp of lithium ion battery.
Preferably, in the process of dilution for the second time, the temperature that keeps slurry is at 40~70 ℃.Effect and control method are as previously mentioned.
Said method is taked unique mixing method; Can be implemented in the equipment and can accomplish whole batch mixing process, the pulp of lithium ion battery of preparation has good uniformity, and; Since better controlled reunion and the size of agglomerated particle of particle; The structure that is difficult to disperse of effectively having avoided conductive agent and rubber powder to form makes that the cell size granularity of preparation is little, good stability, viscosity change for a short time, places not sedimentation for a long time.
Above-mentioned pulp of lithium ion battery can be used for the manufacture batteries pole piece.A kind of preparation method of lithium ion battery comprises above-mentioned pulp of lithium ion battery is coated on the collector, processes the battery positive and negative plate.The electricity core comprises positive plate, negative plate, diaphragm paper, wherein, is provided with diaphragm paper between positive plate and the negative plate, and electric core is put into battery case, injects electrolyte, seals.
Above-mentioned lithium ion battery has following beneficial effect: improved the volume density of the positive and negative plate of battery, improved the uniformity of distribution of particles in the slurry, and then improved capacity and cycle performance, the security performance of lithium ion battery.
Below describe with specific embodiment.
Following examples and Comparative Examples are all accomplished in TXG-50 type three arm planetary mixers.
The preparation of glue:
A certain amount of PVDF powder is distributed in the nmp solvent, disperses to form glue in 2 hours, PVDF solids content scope is 7%.
Embodiment 1:
A certain proportion of graphite and carbon black are put into three arm planetary mixers, under the rotating speed of 5rpm, evenly mix forming powder in 10 minutes.Taking by weighing with the powder quality ratio is 50: 50 NMP.The powder that mixes with after 8% of total NMP mixes one hour, is added remaining 92% NMP again and carries out dilution first time with 35% of total glue, and in chuck, feed 50 hot water of spending and heat flank speed stirring 1 and a half hours.Add remaining 65% glue then and carry out the dilution second time, under low speed, stirred 10 minutes earlier, again at 2 hours pulpings of maximum speed stirring.
Embodiment 2:
With a certain proportion of LiFePO 4Put into three arm planetary mixers with CNT, under the rotating speed of 8rpm, evenly mix forming powder in 30 minutes.Taking by weighing with the powder quality ratio is 55: 4 NMP.The powder that mixes with after 1% of total NMP mixes one hour, is added remaining 99% NMP again and carries out dilution first time with 20% of total glue, and in chuck, feed 40 hot water of spending and heat flank speed stirring 1 and a half hours.Add remaining 80% glue then and carry out the dilution second time, under low speed, stirred 5 minutes earlier, again at 5 hours pulpings of maximum speed stirring.
Embodiment 3:
With a certain proportion of LiNiO 2Put into three arm planetary mixers with carbon fiber, under the rotating speed of 7rpm, evenly mix forming powder in 20 minutes.Taking by weighing with the powder quality ratio is 50: 30 NMP.The powder that mixes with after 5% of total NMP mixes one hour, is added remaining 95% NMP again and carries out dilution first time with 30% of total glue, and in chuck, feed 60 hot water of spending and heat flank speed stirring 100 minutes.Add remaining 70% glue then and carry out the dilution second time, under low speed, stirred 8 minutes earlier, again at 4 hours pulpings of maximum speed stirring.
Embodiment 4:
A certain proportion of lithium nickel cobalt alumina and graphite are put into three arm planetary mixers, under the rotating speed of 6rpm, evenly mix forming powder in 10 minutes.Taking by weighing with the powder quality ratio is 50: 20 NMP.The powder that mixes with after 15% of total NMP mixes one hour, is added remaining 85% NMP again and carries out dilution first time with 50% of total glue, and in chuck, feed 70 hot water of spending and heat flank speed stirring 60 hours.Add remaining 50% glue then and carry out the dilution second time, under low speed, stirred 7 minutes earlier, again at 3 hours pulpings of maximum speed stirring.
Embodiment 5:
A certain proportion of cobalt acid lithium and graphite are put into three arm planetary mixers, under the rotating speed of 6rpm, evenly mix forming powder in 10 minutes.Taking by weighing with the powder quality ratio is 50: 25 NMP.The powder that mixes with after 7% of total NMP mixes one hour, is added remaining 93% NMP again and carries out dilution first time with 25% of total glue, and in chuck, feed 50 hot water of spending and heat flank speed stirring 90 minutes.Add remaining 75% glue then and carry out the dilution second time, under low speed, stirred 9 minutes earlier, again at 2 hours pulpings of maximum speed stirring.
The preparation of glue in the Comparative Examples: a certain amount of PVDF powder is distributed in the nmp solvent, disperses to form glue in 2 hours, the PVDF solids content is 8%.
Comparative Examples 1:
A certain amount of graphite is mixed with the carbon black conductive agent, mixed 1.5 hours, add the residue nmp solution then, disperseed 1 hour, add glue at last and disperse 2 hours pulpings.
Comparative Examples 2:
A certain amount of cobalt acid lithium is mixed with the carbon black conductive agent, disperseed 1.5 hours, add nmp solution then, disperseed 1 hour, add glue at last and disperse 2 hours pulpings.
Slurry test result such as following table that embodiment 1~5 and Comparative Examples 1~2 make.
Sequence number Placed in 24 hours Granularity (μ m) Micelle weight Viscosity changed % in 24 hours
Embodiment 1 No sedimentation ?20 Do not have 7
Embodiment 2 No sedimentation ?23 Do not have 7
Embodiment 3 No sedimentation ?22 Do not have 6
Embodiment 4 No sedimentation ?23 Do not have 5
Embodiment 5 No sedimentation ?25 Do not have 5
Comparative Examples 1 Sedimentation is arranged ?30 Have 22
Comparative Examples 2 Sedimentation is arranged ?35 Serious micelle 20
From experimental result, the slurry that the more traditional method of the method for mixing of the foregoing description makes in the TXG machine is placed not sedimentation for a long time, and viscosity changes little, and granularity is little, and no micelle is with the obvious advantage.
The above embodiment has only expressed several kinds of execution modes of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to claim of the present invention.Should be pointed out that for the person of ordinary skill of the art under the prerequisite that does not break away from the present invention's design, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with accompanying claims.

Claims (10)

1. the preparation method of a pulp of lithium ion battery is characterized in that, comprises the steps:
Step 1, to use bonding agent to prepare concentration be 3%~7% glue;
Step 2, with active material and conductive agent in three arm planetary mixers, under low speed, be uniformly mixed to form powder;
Add in step 3, the powder in step 2 solvent total amount 1%~15%, under low speed, be uniformly mixed to form wet powder, wherein, the total amount of solvent and the mass ratio of said powder are 55: 4~50: 50;
20%~50% and the remaining solvent that add glue in step 4, the wet powder in step 3 evenly mix under at a high speed; And
Step 5, add remaining glue, under low speed, evenly stirred 5~10 minutes earlier, then at stirring 2~5 hours down at a high speed, formation pulp of lithium ion battery.
2. the preparation method of pulp of lithium ion battery according to claim 1, it is characterized in that: said binding agent is a kind of or its mixture in butadiene-styrene rubber, sodium carboxymethylcellulose, Kynoar, polyacrylate, the polyurethane.
3. the preparation method of pulp of lithium ion battery according to claim 1, it is characterized in that: said active material is LiCoO 2, LiMn 2O 4, LiNiO 2, lithium-nickel-cobalt-oxygen, lithium nickel cobalt manganese oxygen, lithium nickel cobalt alumina, LiFePO 4, a kind of or its mixture in graphite, lithium titanate, hard carbon, silicon and the silicon alloy, said conductive agent is a kind of and composition thereof in carbon black, carbon fiber, CNT and the graphite.
4. the preparation method of pulp of lithium ion battery according to claim 1, it is characterized in that: said solvent is water or N-methyl pyrrolidone.
5. the preparation method of pulp of lithium ion battery according to claim 1, it is characterized in that: in the step 2, the time of mixing is 10~30 minutes; In the step 3, the time of mixing is 40~100 minutes.
6. the preparation method of pulp of lithium ion battery according to claim 1, it is characterized in that: step 4 and step 5 are carried out under 40~70 ℃.
7. the preparation method of pulp of lithium ion battery according to claim 1, it is characterized in that: said low speed is 5~8rpm; Said high speed is 22~24rpm.
8. pulp of lithium ion battery of processing by each said preparation method of claim 1~7.
9. battery pole piece of processing by the said pulp of lithium ion battery of claim 8.
10. lithium ion battery that contains the said battery pole piece of claim 9.
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