CN110071288A - Negative electrode slurry and its preparation method and application - Google Patents
Negative electrode slurry and its preparation method and application Download PDFInfo
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- CN110071288A CN110071288A CN201910264882.5A CN201910264882A CN110071288A CN 110071288 A CN110071288 A CN 110071288A CN 201910264882 A CN201910264882 A CN 201910264882A CN 110071288 A CN110071288 A CN 110071288A
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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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- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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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
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- 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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Abstract
The invention discloses a kind of negative electrode slurries and its preparation method and application, this method comprises: negative electrode active material and conductive agent, thickener to be added in three axis planetary mixers and be mixed, obtain the first mixed material；Additive is added into the first mixed material and stirs, obtains the second mixed material；Solvent is added into the second mixed material and stirs under vacuum conditions, obtains the first mixed slurry that solid content is 80wt%~90wt%；Solvent is added into the first mixed slurry and continues to stir under vacuum conditions, obtains the second mixed slurry that solid content is 60wt%~72wt%；Binder and solvent are added into the second mixed slurry and continues to stir under vacuum conditions, obtains the third mixed slurry that solid content is 53wt%~58wt%；Solvent is added into third mixed slurry and continues to stir under vacuum conditions, obtains the negative electrode slurry that viscosity number is 3000~8000mPas.This method can effectively solve the problems, such as the infiltration of stirring initial stage negative electrode active material and solvent, shorten the slurry agitation time, improve the viscosity consistency of slurry.
Description
Technical field
The invention belongs to field of lithium ion battery, specifically, the present invention relates to negative electrode slurry and preparation method thereof and answering
With.
Background technique
To meet the needs of domestic dynamic lithium battery market, major Li electricity manufacturer continues to optimize lithium galvanic process.And
Homogenate stirring technique is the important procedure that lithium battery makes in lithium electricity industry, occupies technical process 30%, plays decisive
Effect, the quality of slurry agitation decides the quality of later period coating and final lithium battery performance.
Lithium battery mainstream enterprise negative (sun) extremely mainly uses copper foil as collector both at home and abroad at present, and graphite system, which is used as, lives
Property substance.Another crucial manufacturing process as lithium ion battery --- painting process is current major lithium power plant commercial city positive
The project improved and researched and developed.Content includes pole piece appearance, coating consistency, dimensional accuracy and excellent rate etc., and wherein cathode is coated with
Appearance and excellent rate are one of the projects challenged the most.Since negative electrode slurry uses water-based system, graphite itself, which has, certain hates
It is aqueous.For use deionized water is as the negative electrode slurry of solvent, water has certain difficulty to the infiltration of graphite, especially
It is, specific surface area biggish graphite small for some partial sizes, it is each to will appear particle scratch, bubble, stain, point etc. in coating
Kind bad order, and seriously affect product excellent rate.Therefore, the quality of negative electrode slurry directly determines the good of coated product quality
It is bad, because of this, the stirring and processing technique of negative electrode slurry becomes the research of major lithium power plant quotient main attack also with regard to ever more important
Direction.
In order to solve the problems, such as the bad order and excellent rate of appeal cathode coating, currently, there are mainly two types of solve for agitating procedure
Mode: the first is to improve negative electrode slurry dispersibility, such as take high speed dispersion, mediate stirring proportioning process, and high speed dispersion is not
Only mixing time is long, energy consumption is high and has certain destruction to organic polymers such as stabilizer, binders in formula, thus
Influence the stability and pole piece cohesive force of slurry；Stirring is mediated for currently used double planetary mixer, because of the paddle that revolves
Torsional forces it is not powerful enough, the solid content of kneading is required, if solid content is excessively high, viscosity resistance is too big, will lead to revolution paddle
It can not rotate.Second is the composition for changing negative electrode slurry, and addible component often remains in pole piece, leads to battery core
It can be affected, while its improvement is unstable, need to be repeated.
Therefore, the preparation method of existing negative electrode slurry is further improved.
Summary of the invention
The present invention is directed to solve at least some of the technical problems in related technologies.For this purpose, of the invention
One purpose is to propose a kind of negative electrode slurry and its preparation method and application.It is living that this method can effectively solve stirring initial stage cathode
The infiltration problem of property material and solvent, while can significantly shorten the slurry agitation time, and improve the viscosity consistency of slurry.
In one aspect of the invention, the invention proposes a kind of method for preparing negative electrode slurry, realities according to the present invention
Example is applied, this method comprises:
(1) negative electrode active material and conductive agent, thickener are added in three axis planetary mixers and are mixed, so as to
Obtain the first mixed material；
(2) additive is added in the first mixed material of Xiang Suoshu and stirs, to obtain the second mixed material；
(3) solvent is added in the second mixed material of Xiang Suoshu and stirs under vacuum conditions, is to obtain solid content
The first mixed slurry of 80wt%~90wt%；
(4) solvent is added in the first mixed slurry of Xiang Suoshu and continues to stir under vacuum conditions, to be consolidated
Content is the second mixed slurry of 60wt%~72wt%；
(5) binder and the solvent are added in the second mixed slurry of Xiang Suoshu and continues to stir under vacuum conditions, with
Just the third mixed slurry that solid content is 53wt%~58wt% is obtained；
(6) solvent is added in Xiang Suoshu third mixed slurry and continues to stir under vacuum conditions, to be glued
Angle value is the negative electrode slurry of 3000~8000mPas.
The method according to an embodiment of the present invention for preparing negative electrode slurry, by by negative electrode active material and conductive agent, thickening
Agent is supplied to three axis planetary mixers and is mixed, and realizes the micromixing between powder, and it is right in subsequent high viscous stirring to be conducive to
The infiltration of opening and powder granule surface that powder granule is reunited.The mixing simultaneously carries out in three axis planetary mixers,
Relative to traditional double planetary mixer without high speed dispersion dish, high speed dispersion dish are avoided to thickener molecule structure in slurry
High speed shear damage and the destruction to subsequent binder are conducive to improve the stability of slurry and the cohesive force of pole piece.Further
, three axis planetary mixers revolution paddle than double-planet revolution paddle torsional forces it is powerful, be conducive to powder particles surface infiltration,
The shearing kneading of slurry acts on, and then shortens mixing time, while viscous mediate of the height that can do more high solids content is stirred.Additive
Be conducive to improve the wellability on powder granule surface, and then be conducive to the dispersion of powder granule after subsequent addition solvent.Control first
The solid content of mixed slurry is 80wt%~90wt%, is conducive to improve the shearing friction effect between powder granule, Jin Erjin
One step promotes particle surface wetting.The second mixed slurry solid content is controlled to be 60wt%~72wt% and combine three axis planet stirrings
The high-intensitive shearing kneading effect of machine is conducive to agglomerated particle so that the kneading shear action between wetting powder granule is very strong
Dispersion, meanwhile, powerful kneading shear action makes thickener particle start to remove dissolution from level to level.Control third mixed slurry
Solid content be 53wt%~58wt%, under the high-intensitive shearing kneading effect of three axis planetary mixers, be conducive to binder
Preferably be scattered in solvent with particle, promote being completely dissolved for thickener, be uniformly dispersed and stable slurry, then into
Row adjusts the viscous negative electrode slurry for obtaining viscosity number as 3000~8000mPas.It can effectively be solved by using the above method as a result,
The infiltration problem of stirring initial stage negative electrode active material and solvent, while can significantly shorten the slurry agitation time, and improve slurry
Viscosity consistency.
In addition, the method according to the above embodiment of the present invention for preparing negative electrode slurry can also have following additional technology
Feature:
In some embodiments of the invention, in step (1), the revolution speed of the three axis planetary mixer is 5~
10rpm, rotational velocity are 15~30rpm, and mixing time is 5~10min.It can further improve the macroscopic view between powder as a result,
Mixing efficiency.
In some embodiments of the invention, the negative electrode active material and the conductive agent, described in step (1)
The mass ratio of thickener is (92~98): (0.5~4): (0.5~2).It can further improve the quality of negative electrode slurry as a result,.
In some embodiments of the invention, in step (1), the negative electrode active material is selected from artificial graphite, day
At least one of right graphite, hard carbon, soft carbon.It can further improve the quality of negative electrode slurry as a result,.
In some embodiments of the invention, in step (1), the conductive agent is selected from super conductive carbon, carbon nanometer
At least one of pipe, graphene and electrically conductive graphite.It can further improve the quality of negative electrode slurry as a result,.
In some embodiments of the invention, in step (1), the thickener is in selection CMC powder, CMC solution
At least one of.It can further improve the quality of negative electrode slurry as a result,.
In some embodiments of the invention, in step (2), the revolution speed of the three axis planetary mixer is 5~
15rpm, rotational velocity are 15~45rpm, and mixing time is 10~20min, and whipping temp is 0 DEG C~40 DEG C.It as a result, can be into one
Step improves the mixed effect of additive and the first mixed material.
In some embodiments of the invention, in step (2), the additive is selected from acetone, ethyl alcohol, 1,3- fourth two
At least one of alcohol, NMP.Powder granule wettability of the surface can further be improved as a result,.
In some embodiments of the invention, in step (2), the quality of the additive and first mixed material
Than for (0.1~5): 100.Powder granule wettability of the surface can further be improved as a result,.
In some embodiments of the invention, in step (3), the revolution speed of the three axis planetary mixer is 5~
20rpm, rotational velocity are 15~60rpm, and mixing time is 10~15min, and whipping temp is 55 DEG C~70 DEG C.It as a result, can be into
One step improves the shearing friction effect between powder granule.
In some embodiments of the invention, in step (3), the solvent be deionized water, in NMP at least it
One.It can further improve the quality of negative electrode slurry.
In some embodiments of the invention, in step (4), the revolution speed of the three axis planetary mixer is 15~
25rpm, rotational velocity are 45~75rpm, and mixing time is 40~65min, and whipping temp is 55 DEG C~70 DEG C.It as a result, can be into
One step promotes agglomerated particle dispersion and the removing of thickener dissolution.
In some embodiments of the invention, in step (5), the revolution speed of the three axis planetary mixer is 5~
20rpm, rotational velocity are 15~60rpm, and mixing time is 25~35min, and whipping temp is 20 DEG C~35 DEG C.It as a result, can be into
One step promotes binder and particle to be scattered in solvent.
In some embodiments of the invention, in step (5), the binder is in SBR, LA132, LA133
At least one of.It can further improve the quality of negative electrode slurry as a result,.
In some embodiments of the invention, in step (5), the quality of the binder and first mixed material
Than for (1~5): 100.It can further improve the quality of negative electrode slurry as a result,.
In some embodiments of the invention, in step (6), the revolution speed of the three axis planetary mixer is 5~
15rpm, rotational velocity are 15~45rpm, and mixing time is 25~35min, and whipping temp is 20 DEG C~35 DEG C.It is advantageous as a result,
Viscous rate is adjusted in improving.
In some embodiments of the invention, in step (3), step (4), step (5), step (6), the vacuum item
The vacuum degree of part is separately -90~-30kPa.It can further improve the quality of negative electrode slurry as a result,.
In another aspect of the invention, the invention proposes a kind of negative electrode slurries, according to an embodiment of the invention, described
Negative electrode slurry is prepared using the above-mentioned method for preparing negative electrode slurry.Each component particle point in the negative electrode slurry as a result,
It dissipates uniformly, viscosity consistency with higher and stability are conducive to the coating appearance for improving the slurry and cohesive force.
In an additional aspect of the present invention, the invention proposes a kind of lithium ion batteries, according to an embodiment of the invention, institute
The cathode for stating lithium ion battery is prepared using above-mentioned negative electrode slurry.Negative electrode slurry and collector in cathode as a result,
Cohesive force is stronger, and because in negative electrode slurry each component particle be uniformly dispersed, may make cathode have preferable charge-discharge performance, into
And it is remarkably improved the performance of lithium ion battery, while because of negative electrode slurry lower production costs, lithium-ion electric can be further decreased
The cost in pond.
Additional aspect and advantage of the invention will be set forth in part in the description, and will partially become from the following description
Obviously, or practice through the invention is recognized.
Detailed description of the invention
Above-mentioned and/or additional aspect of the invention and advantage will become from the description of the embodiment in conjunction with the following figures
Obviously and it is readily appreciated that, in which:
Fig. 1 is the method flow schematic diagram according to an embodiment of the invention for preparing negative electrode slurry.
Specific embodiment
The embodiment of the present invention is described below in detail, examples of the embodiments are shown in the accompanying drawings, wherein from beginning to end
Same or similar label indicates same or similar element or element with the same or similar functions.Below with reference to attached
The embodiment of figure description is exemplary, it is intended to is used to explain the present invention, and is not considered as limiting the invention.
In addition, term " first ", " second " are used for descriptive purposes only and cannot be understood as indicating or suggesting relative importance
Or implicitly indicate the quantity of indicated technical characteristic.Define " first " as a result, the feature of " second " can be expressed or
Implicitly include at least one this feature.In the description of the present invention, the meaning of " plurality " is at least two, such as two, three
It is a etc., unless otherwise specifically defined.
In one aspect of the invention, the invention proposes a kind of method for preparing negative electrode slurry, realities according to the present invention
Example is applied, with reference to Fig. 1, this method comprises:
S100: negative electrode active material and conductive agent, thickener are added in three axis planetary mixers and are mixed
In the step, negative electrode active material is added in three axis planetary mixers with conductive agent, thickener and mix stirring
It mixes, to obtain the first mixed material.Inventors have found that by supplying negative electrode active material and conductive agent, thickener to three
Axis planetary mixer is mixed, and realizes the micromixing between powder, is conducive in subsequent high viscous stirring to powder granule group
The infiltration of poly- opening and powder granule surface.The mixing simultaneously carries out in three axis planetary mixers, relative to tradition
Double planetary mixer without high speed dispersion dish, avoid high speed dispersion dish and the high speed shear of thickener molecule structure in slurry damaged
The bad and destruction to subsequent binder is conducive to improve the stability of slurry and the cohesive force of pole piece.Further, three axis planet
The revolution paddle of blender is more powerful than the torsional forces of double-planet revolution paddle, is conducive to surface infiltration, the shearing of slurry of powder particles
Kneading effect, and then shorten mixing time, while viscous mediate of height that can do more high solids content is stirred.
According to one embodiment of present invention, the revolution speed of three axis planetary mixers can be 5~10rpm, from revolving speed
Degree can be 15~30rpm, and mixing time can be 5~10min.Specifically, the revolution speed of three axis planetary mixers can be with
For 5rpm, 6rpm, 7rpm, 8rpm, 9rpm, 10rpm；Rotational velocity can for 15rpm, 17rpm, 20rpm, 22rpm, 25rpm,
28rpm,30rpm；Time can be 5min, 6min, 7min, 8min, 9min, 10min.Inventors have found that by using having
Three axis planetary mixers of high shear forces can significantly reduce the mixing speed in whipping process and time, improve negative electrode slurry
Preparation efficiency.If the revolving speed of the revolution of three axis planetary mixers and/or rotation is excessively high, it is very big to will lead to powder fugitive dust, and make
The light powder of density is distributed in top, and the powder of density weight is distributed in lower part, and the macroscopic view being unfavorable between powder mixes；And if three
The revolving speed of revolution and/or the rotation of axis planetary mixer is too low, then macroscopic view, which mixes, just needs the too long time.It needs to illustrate
It is that revolution speed, the rotational velocity of three axis planetary mixers described in this paper respectively refer to the public affairs of agitating paddle in three axis planetary mixers
Rotary speed and rotational velocity.
Still another embodiment in accordance with the present invention, negative electrode active material and conductive agent, thickener mass ratio not by spy
It does not limit, those skilled in the art can select according to actual needs, such as can be (92~98): (0.5~4):
(0.5~2).Further, such as can be (92/93/94/95/96/97/98): (0.5/1/1.5/2/2.5/3/3.5/4):
(0.5/1.0/1.5/2.0).It should be noted that the concrete content of negative electrode active material, conductive agent, thickener each component can be with
According to equlibrated slurry stability, rheological characteristic, the manufacturabilitys such as pole piece densification, cohesive force and the subsequent electrical property for preparing battery be can be carried out
It determines.Specifically, negative electrode active material can be to lead selected from least one of artificial graphite, natural graphite, hard carbon, soft carbon
Electric agent can be for selected from least one of super conductive carbon, carbon nanotube, graphene and electrically conductive graphite, thickener can be choosing
Select at least one of CMC powder, CMC solution.Inventors have found that above-mentioned negative electrode active material capacity, using cycle life and
Price is more excellent；Above-mentioned conductive agent electric conductivity is excellent, to battery electrical property without other side effects, while use cost compared with
It is low；Thickening effect is obvious in a solvent for above-mentioned thickener, for improving Stability of Slurry excellent effect, meanwhile, thickener contains
It measures smaller to the side effect of battery electrical property within the above range.
S200: additive is added into the first mixed material and stirs
In the step, additive is added into the first mixed material and stirs, to obtain the second mixed material.Inventor
It was found that additive is conducive to improve the wellability on powder granule surface, and then it is conducive to point of powder granule after subsequent addition solvent
It dissipates.Specifically, additive can be selected from least one of acetone, ethyl alcohol, 1,3-BDO, NMP, and additive and first
The mass ratio of mixed material can be (0.1~5): 100, such as can be (0.1/0.5/1.0/1.5/2.0/2.5/3.0/
3.5/4.0/4.5/5.0): 100.Inventors have found that additive acetone, ethyl alcohol, 1,3-BDO, NMP and negative electrode active material
Contact angle it is small, it is easy to infiltrated with negative electrode active material, while above-mentioned additive is easy to volatilize, and holds very much in subsequent painting process
It is volatile to go out, pole piece will not be remained on, the electrical property of battery is not influenced.
According to one embodiment of present invention, the revolution speed of three axis planetary mixers can be 5~15rpm, from revolving speed
Degree can be 15~45rpm, and mixing time can be 10~20min, and whipping temp can be 0 DEG C~40 DEG C.Specifically, three axis
The revolution speed of planetary mixer can be 5rpm, 7rpm, 9rpm, 11rpm, 13rpm, 15rpm；Rotational velocity can be
15rpm,20rpm,25rpm,30rpm,35rpm,40rpm,45rpm；Time can for 10min, 12min, 14min, 16min,
18min,20min；Temperature can be 0 DEG C, 5 DEG C, 10 DEG C, 15 DEG C, 20 DEG C, 25 DEG C, 30 DEG C, 35 DEG C, 40 DEG C.The temperature of stirring can
It is controlled in method by the thermostatical circulating water for being passed through relevant temperature in three axis planetary mixer interlayers.In above-mentioned temperature model
The diffusion motion of each group fractionated molecule in powder can be made more violent in enclosing, to promote the mixing of powder granule and additive.Invention
People's discovery, if the revolving speed of revolution and the rotation of three axis planetary stirrers is too high, machine utilization is too heavy, and three axis planets may be made to stir
The agitating paddle for mixing device can not rotate or heat production abrasion it is too big, and if the revolution of three axis planetary stirrers and autobiography revolving speed too
Low, then mixing time extends, efficiency is too low and mixing effect is bad；If the temperature of stirring is too low, it is unfavorable for additive molecule expansion
Dissipate, and then influence the wetting of negative electrode material, and if temperature is excessively high that additive can be made quickly to volatilize, also will affect negative when subsequent stirring
The infiltration of pole material.
S300: solvent is added into the second mixed material and stirs under vacuum conditions
In the step, solvent is added into the second mixed material and stirs under vacuum conditions, is to obtain solid content
The first mixed slurry of 80wt%~90wt%.Specifically, the solid content of the first mixed slurry can for 80wt%, 82wt%,
84wt%, 86wt%, 88wt%, 90wt%.Solvent can be at least one of deionized water, NMP.Inventors have found that control
The solid content for making the first mixed slurry is 80wt%~90wt%, is conducive to improve the shearing friction effect between powder granule,
And then further particle surface is promoted to soak.Solvent can significantly reduce production cost using deionized water, while can also expire
Sufficient slurry quality demand；In addition the NMP small with negative electrode active material contact angle can also be used, can be very good to improve wellability,
Conducive to the negative electrode slurry for obtaining higher quality.
According to one embodiment of present invention, the revolution speed of three axis planetary mixers can be 5~20rpm, from revolving speed
Degree can be 15~60rpm, and mixing time can be 10~15min, and whipping temp can be 55 DEG C~70 DEG C, vacuum condition
Vacuum degree can be -90~-30kPa.Specifically, the revolution speed of three axis planetary mixers can for 5rpm, 7rpm, 10rpm,
12rpm,15rpm,17rpm,20rpm；Rotational velocity can for 15rpm, 20rpm, 25rpm, 30rpm, 35rpm, 40rpm,
45rpm,50rpm,55rpm,60rpm；Time can be 10min, 11min, 12min, 13min, 14min, 15min；Temperature can
Think 55 DEG C, 57 DEG C, 60 DEG C, 62 DEG C, 65 DEG C, 67 DEG C, 70 DEG C；Vacuum degree can for -90kPa, -85kPa, -80kPa, -
75kPa,-70kPa,-65kPa,-60kPa,-55kPa,-50kPa,-45kPa,-40kPa,-35kPa,-30kPa.The temperature of stirring
Degree can be controlled by the method for being passed through in three axis planetary mixer interlayers the thermostatical circulating water of relevant temperature.Invention human hair
It is existing, it is stirred at the temperature disclosed above, can both increase the contact between solvent molecule of powder particles surface, promote powder particles
Diffusion in a solvent is conducive to wetting, simultaneously as the presence of solvent, additive easily dissolve each other with solvent, can avoid additive
Volatilization.If the revolving speed of revolution and the rotation of three axis planetary stirrers is too high, machine utilization is too heavy, may make three axis planet stirrings
The agitating paddle of device can not rotate or heat production abrasion it is too big, and if the revolution of three axis planetary stirrers and autobiography revolving speed are too low,
Then mixing time extends, efficiency is too low and mixing effect is bad；If the temperature of stirring is excessively high, will lead to macromolecule in slurry at
Separation structure is deformed or is destroyed, and excessively high temperature has requirements at the higher level to the sealing of equipment and bearing strength, and temperature is too low then
The effect for promoting powder granule infiltration is not achieved.The main purpose of vacuum environment is the bubble removed in powder particles and slurry,
The too high requirement to equipment of vacuum level requirements will improve, and the too low purpose that bubble removing can be not achieved of vacuum degree.
S400: solvent is added into the first mixed slurry and continues to stir under vacuum conditions
In the step, solvent is added into the first mixed slurry and continues to stir under vacuum conditions, to be contained admittedly
Amount is the second mixed slurry of 60wt%~72wt%.Specifically, the solid content of the second mixed slurry can for 60wt%,
62wt%, 64wt%, 66wt%, 68wt%, 70wt%, 72wt%.Inventors have found that the second mixed slurry solid content of control is
60wt%~72wt% and the high-intensitive shearing kneading effect for combining three axis planetary mixers, so that pinching between wetting powder granule
It is very strong to close shear action, is conducive to agglomerated particle dispersion, meanwhile, powerful kneading shear action starts thickener particle
Removing dissolution from level to level.
According to one embodiment of present invention, the revolution speed of three axis planetary mixers can be 15~25rpm, from revolving speed
Degree can be 45~75rpm, and mixing time can be 40~65min, and whipping temp can be 55 DEG C~70 DEG C, vacuum condition
Vacuum degree can be -90~-30kPa.Specifically, the revolution speed of three axis planetary mixers can for 15rpm, 18rpm,
20rpm,23rpm,25rpm；Rotational velocity can be 45rpm, 50rpm, 55rpm, 60rpm, 65rpm, 70rpm, 75rpm；When
Between can be 40min, 45min, 50min, 55min, 60min；Temperature can be 55 DEG C, 57 DEG C, 60 DEG C, 62 DEG C, 65 DEG C, 67
℃,70℃；Vacuum degree can for -90kPa, -85kPa, -80kPa, -75kPa, -70kPa, -65kPa, -60kPa, -55kPa, -
50kPa,-45kPa,-40kPa,-35kPa,-30kPa.The temperature of stirring can be by leading in three axis planetary mixer interlayers
Enter the method for the thermostatical circulating water of relevant temperature to control.Inventors have found that being stirred within the said temperature range, more favorably
It is dissolved in the removing of thickener.If the revolving speed of revolution and the rotation of three axis planetary stirrers is too high, machine utilization is too heavy, may make
Three axis planetary stirrers agitating paddle rotate not get up or heat production abrasion it is too big, and if the revolution of three axis planetary stirrers with
Autobiography revolving speed is too low, then mixing time extends, efficiency is too low and mixing effect is bad；If the temperature of stirring is excessively high, slurry will lead to
Macromolecule component malformation in material is destroyed, and excessively high temperature has higher want to the sealing of equipment and bearing strength
It asks, and temperature is too low, and enhancement particle agglomeration is not achieved and breaks up the effect dissolved with thickener.The main purpose of vacuum environment is
The bubble in powder particles and slurry is removed, the too high requirement to equipment of vacuum level requirements will improve, and the too low meeting of vacuum degree
The purpose of bubble removing is not achieved.
S500: binder and solvent are added into the second mixed slurry and continues to stir under vacuum conditions
In the step, binder and solvent are added into the second mixed slurry and continues to stir under vacuum conditions, so as to
Obtain the third mixed slurry that solid content is 53wt%~58wt%.Specifically, the solid content of third mixed slurry can be
53wt%, 54wt%, 55wt%, 56wt%, 57wt%, 58wt%.Binder can be in SBR, LA132, LA133
At least one.The mass ratio of binder and the first mixed material can be (1~5): 100, such as can be 1:100,2:100,
3:100,4:100,5:100.Inventors have found that the solid content of control third mixed slurry is 53wt%~58wt%, in three axis
Under the high-intensitive shearing kneading effect of planetary mixer, is conducive to binder and particle is preferably scattered in solvent, promote to increase
Thick dose is completely dissolved, and is uniformly dispersed and stable slurry.Binder SBR, LA132, LA133 can be highly stable deposit
It is in water solvent or oil system nmp solvent, while can makes to possess between negative electrode active material and copper foil base material viscous well
Power is tied, and the adverse effect that the additive amount of binder plays the electrical property of battery in above-mentioned mass range is very low, it is very suitable
Cooperation is the binder of cathode.
According to one embodiment of present invention, the revolution speed of three axis planetary mixers can be 5~20rpm, from revolving speed
Degree can be 15~60rpm, and mixing time can be 25~35min, and whipping temp can be 20 DEG C~35 DEG C, vacuum condition
Vacuum degree can be -90~-30kPa.Specifically, the revolution speed of three axis planetary mixers can for 5rpm, 8rpm, 10rpm,
13rpm,15rpm,17rpm,20rpm；Rotational velocity can for 15rpm, 20rpm, 25rpm, 30rpm, 35rpm, 40rpm,
45rpm,50rpm,55rpm,60rpm；Time can be 25min, 28min, 30min, 33min, 35min；Temperature can be 20
℃,25℃,30℃,35℃；Vacuum degree can for -90kPa, -85kPa, -80kPa, -75kPa, -70kPa, -65kPa, -
60kPa,-55kPa,-50kPa,-45kPa,-40kPa,-35kPa,-30kPa.The temperature of stirring can pass through past three axis planets
The method of the thermostatical circulating water of relevant temperature is passed through in blender interlayer to control.Inventors have found that above-mentioned temperature mainly makes
Slurry temperature cools down, and improves the discharging viscosity consistency of slurry.If the revolving speed of revolution and the rotation of three axis planetary stirrers
Too high, machine utilization is too heavy, may make the agitating paddle of three axis planetary stirrers can not rotate or heat production abrasion it is too big, and
If the revolution of three axis planetary stirrers and autobiography revolving speed are too low, mixing time extends, efficiency is too low and mixing effect is bad；If
The temperature of stirring is excessively high, is unfavorable for the control of subsequent slurry shipment temperature, influences viscosity consistency when slurry shipment, and temperature
It is too low to will affect mixing effect, in addition, energy consumption needed for the too low stirring of temperature will increase, and equally it is unfavorable for controlling the glutinous of slurry
Degree and consistency.The main purpose of vacuum environment is the bubble removed in powder particles and slurry, and vacuum level requirements are too high to setting
Standby requirement will improve, and the too low purpose that bubble removing can be not achieved of vacuum degree.
S600: solvent is added into third mixed slurry and continues to stir under vacuum conditions
In the step, solvent is added into third mixed slurry and continues to stir under vacuum conditions, to obtain viscosity
Value be 3000~8000mPas negative electrode slurry, such as available viscosity number be 3000mPas, 3500mPas,
4000mPa·s、4500mPa·s、5000mPa·s、5500mPa·s、6000mPa·s、6500mPa·s、7000mPa·s、
7500mPa·s,8000mPa·s.Specifically, the viscosity number of negative electrode slurry can be according to the stability of slurry and the demand of coating
It determines.
According to one embodiment of present invention, the revolution speed of three axis planetary mixers can be 5~15rpm, from revolving speed
Degree can be 15~45rpm, and mixing time can be 25~35min, and whipping temp can be 20 DEG C~35 DEG C, vacuum condition
Vacuum degree can be -90~-30kPa.Specifically, the revolution speed of three axis planetary mixers can for 5rpm, 7rpm, 10rpm,
12rpm,15rpm；Rotational velocity can be 15rpm, 20rpm, 25rpm, 30rpm, 35rpm, 40rpm, 45rpm；Time can be with
For 25min, 28min, 30min, 32min, 35min；Temperature can be 20 DEG C, 25 DEG C, 30 DEG C, 35 DEG C；Vacuum degree can for-
90kPa、-85kPa、-80kPa、-75kPa、-70kPa、-65kPa、-60kPa、-55kPa、-50kPa、-45kPa、-40kPa、-
35kPa,-30kPa.The temperature of stirring can be by being passed through the thermostatical circulating water of relevant temperature in three axis planetary mixer interlayers
Method control.Inventors have found that machine utilization is too heavy if the revolving speed of revolution and the rotation of three axis planetary stirrers is too high,
It may make that the agitating paddles of three axis planetary stirrers can not rotate or heat production abrasion is too big, and if three axis planetary stirrers
Revolution and autobiography revolving speed are too low, then mixing time extends, efficiency is too low and mixing effect is bad；If the temperature of stirring is excessively high, no
Conducive to the control of slurry viscosity and the consistency of realization slurry, and temperature is too low, influences mixing effect, stirs in addition, temperature is too low
Mixing required energy consumption will increase, and equally be unfavorable for controlling the viscosity and consistency of slurry.The main purpose of vacuum environment is
Except the bubble in powder particles and slurry, the too high requirement to equipment of vacuum level requirements will be improved, and vacuum degree is too low to reach
Less than the purpose for removing bubble removing.
The method according to an embodiment of the present invention for preparing negative electrode slurry, by by negative electrode active material and conductive agent, thickening
Agent is supplied to three axis planetary mixers and is mixed, and realizes the micromixing between powder, and it is right in subsequent high viscous stirring to be conducive to
The infiltration of opening and powder granule surface that powder granule is reunited.The mixing simultaneously carries out in three axis planetary mixers,
Relative to traditional double planetary mixer without high speed dispersion dish, high speed dispersion dish are avoided to thickener molecule structure in slurry
High speed shear damage and the destruction to subsequent binder are conducive to improve the stability of slurry and the cohesive force of pole piece.Further
, three axis planetary mixers revolution paddle than double-planet revolution paddle torsional forces it is powerful, be conducive to powder particles surface infiltration,
The shearing kneading of slurry acts on, and then shortens mixing time, while viscous mediate of the height that can do more high solids content is stirred.Additive
Be conducive to improve the wellability on powder granule surface, and then be conducive to the dispersion of powder granule after subsequent addition solvent.Control first
The solid content of mixed slurry is 80wt%~90wt%, is conducive to improve the shearing friction effect between powder granule, Jin Erjin
One step promotes particle surface wetting.The second mixed slurry solid content is controlled to be 60wt%~72wt% and combine three axis planet stirrings
The high-intensitive shearing kneading effect of machine is conducive to agglomerated particle so that the kneading shear action between wetting powder granule is very strong
Dispersion, meanwhile, powerful kneading shear action makes thickener particle start to remove dissolution from level to level.Control third mixed slurry
Solid content be 53wt%~58wt%, under the high-intensitive shearing kneading effect of three axis planetary mixers, be conducive to binder
Preferably be scattered in solvent with particle, promote being completely dissolved for thickener, be uniformly dispersed and stable slurry, then into
Row adjusts the viscous negative electrode slurry for obtaining viscosity number as 3000~8000mPas.It can effectively be solved by using the above method as a result,
The infiltration problem of stirring initial stage negative electrode active material and solvent, while can significantly shorten the slurry agitation time, and improve slurry
Viscosity consistency.
In another aspect of the invention, the invention proposes a kind of negative electrode slurries, according to an embodiment of the invention, described
Negative electrode slurry is prepared using the above-mentioned method for preparing negative electrode slurry.Each component particle point in the negative electrode slurry as a result,
It dissipates uniformly, viscosity consistency with higher and stability are conducive to the coating appearance for improving the slurry and cohesive force.It needs
It is bright, it is above-mentioned to be equally applicable to the negative electrode slurry for preparing feature and advantage described in the method for negative electrode slurry, herein
It repeats no more.
In an additional aspect of the present invention, the invention proposes a kind of lithium ion batteries, according to an embodiment of the invention, institute
The cathode for stating lithium ion battery is prepared using above-mentioned negative electrode slurry.Negative electrode slurry and collector in cathode as a result,
Cohesive force is stronger, and because in negative electrode slurry each component particle be uniformly dispersed, may make cathode have preferable charge-discharge performance, into
And it is remarkably improved the performance of lithium ion battery, while because of negative electrode slurry lower production costs, lithium-ion electric can be further decreased
The cost in pond.It should be noted that above-mentioned be equally applicable to the lithium-ion electric for feature and advantage described in negative electrode slurry
Pond, details are not described herein again.
Below with reference to specific embodiment, present invention is described, it should be noted that these embodiments are only to describe
Property, without limiting the invention in any way.
Embodiment 1
(1) by negative electrode active material artificial graphite and the super conductive carbon of conductive agent, thickener CMC powder according to mass ratio
96.5:1.0:1.0 is added in three axis planetary mixers and is mixed, and the revolution speed of three axis planetary mixers is 8rpm,
Rotational velocity is 24rpm, and mixing time 9min obtains the first mixed material；
(2) it is added and additive 1,3-BDO and stirs into the first mixed material, additive and the first mixed material
Mass ratio is 0.5:100, and the revolution speed of three axis planetary mixers is 10rpm, rotational velocity 30rpm, and mixing time is
10min, whipping temp are 25 DEG C, obtain the second mixed material；
(3) solvent deionized water is added into the second mixed material and stirs under vacuum conditions, three axis planetary mixers
Revolution speed be 15rpm, rotational velocity 45rpm, mixing time 10min, whipping temp be 60 DEG C, vacuum condition it is true
Reciprocal of duty cycle is -90kPa, obtains the first mixed slurry that solid content is 86wt%；
(4) solvent deionized water is added into the first mixed slurry and continues to stir under vacuum conditions, three axis planets stir
The revolution speed for mixing machine is 20rpm, rotational velocity 60rpm, mixing time 50min, and whipping temp is 60 DEG C, vacuum condition
Vacuum degree be -90kPa, obtain solid content be 67wt% the second mixed slurry；
(5) binder SBR emulsion and solvent deionized water are added into the second mixed slurry and continues under vacuum conditions
The mass ratio of stirring, binder SBR emulsion and the first mixed material is 1.5:100, and the revolution speed of three axis planetary mixers is
10rpm, rotational velocity 30rpm, mixing time 30min, whipping temp are 25 DEG C, the vacuum degree of vacuum condition is-
90kPa obtains the third mixed slurry that solid content is 56wt%；
(6) solvent deionized water is added into third mixed slurry and continues to stir under vacuum conditions, three axis planets stir
The revolution speed for mixing machine is 15rpm, rotational velocity 45rpm, mixing time 25min, and whipping temp is 25 DEG C, vacuum condition
Vacuum degree be -90kPa, obtain viscosity number be 6000mPas negative electrode slurry, the testing result of the negative electrode slurry such as 1 institute of table
Show.
In each step, the temperature of stirring is the constant temperature circulating by being passed through relevant temperature in three axis planetary mixer interlayers
The method of water controls.
Embodiment 2
(1) by negative electrode active material natural graphite and conductive agent carbon nanotube, thickener CMC powder according to mass ratio 92:
4:2 is added in three axis planetary mixers and is mixed, and the revolution speed of three axis planetary mixers is 5rpm, and rotational velocity is
30rpm, mixing time 5min obtain the first mixed material；
(2) additive acetone is added into the first mixed material and stirs, the mass ratio of additive and the first mixed material
For 0.1:100, the revolution speed of three axis planetary mixers is 5rpm, rotational velocity 45rpm, mixing time 15min, stirring
Temperature is 0 DEG C, obtains the second mixed material；
(3) solvent deionized water is added into the second mixed material and stirs under vacuum conditions, three axis planetary mixers
Revolution speed be 5rpm, rotational velocity 60rpm, mixing time 12min, whipping temp be 55 DEG C, vacuum condition it is true
Reciprocal of duty cycle is -70kPa, obtains the first mixed slurry that solid content is 80wt%；
(4) solvent deionized water is added into the first mixed slurry and continues to stir under vacuum conditions, three axis planets stir
The revolution speed for mixing machine is 15rpm, rotational velocity 75rpm, mixing time 40min, and whipping temp is 55 DEG C, vacuum condition
Vacuum degree be -70kPa, obtain solid content be 60wt% the second mixed slurry；
(5) binder SBR emulsion and solvent deionized water are added into the second mixed slurry and continues under vacuum conditions
The mass ratio of stirring, binder SBR emulsion and the first mixed material is 1:100, and the revolution speed of three axis planetary mixers is
5rpm, rotational velocity 60rpm, mixing time 25min, whipping temp are 20 DEG C, and the vacuum degree of vacuum condition is -70kPa,
Obtain the third mixed slurry that solid content is 53wt%；
(6) solvent deionized water is added into third mixed slurry and continues to stir under vacuum conditions, three axis planets stir
The revolution speed for mixing machine is 10rpm, rotational velocity 30rpm, mixing time 30min, and whipping temp is 20 DEG C, vacuum condition
Vacuum degree be -70kPa, obtain viscosity number be 3000mPas negative electrode slurry, the testing result of the negative electrode slurry such as 1 institute of table
Show.
In each step, the temperature of stirring is the constant temperature circulating by being passed through relevant temperature in three axis planetary mixer interlayers
The method of water controls.
Embodiment 3
(1) by negative electrode active material hard carbon and conductive agent graphene, thickener CMC powder according to mass ratio 98:0.5:0.5
It is added in three axis planetary mixers and is mixed, the revolution speed of three axis planetary mixers is 10rpm, and rotational velocity is
15rpm, mixing time 10min obtain the first mixed material；
(2) additive ethyl alcohol is added into the first mixed material and stirs, the mass ratio of additive and the first mixed material
For 5:100, the revolution speed of three axis planetary mixers is 15rpm, rotational velocity 15rpm, mixing time 20min, stirring
Temperature is 40 DEG C, obtains the second mixed material；
(3) solvent deionized water is added into the second mixed material and stirs under vacuum conditions, three axis planetary mixers
Revolution speed be 20rpm, rotational velocity 15rpm, mixing time 15min, whipping temp be 70 DEG C, vacuum condition it is true
Reciprocal of duty cycle is -60kPa, obtains the first mixed slurry that solid content is 90wt%；
(4) solvent deionized water is added into the first mixed slurry and continues to stir under vacuum conditions, three axis planets stir
The revolution speed for mixing machine is 25rpm, rotational velocity 45rpm, mixing time 65min, and whipping temp is 70 DEG C, vacuum condition
Vacuum degree be -60kPa, obtain solid content be 72wt% the second mixed slurry；
(5) binder SBR emulsion and solvent deionized water are added into the second mixed slurry and continues under vacuum conditions
The mass ratio of stirring, binder SBR emulsion and the first mixed material is 5:100, and the revolution speed of three axis planetary mixers is
20rpm, rotational velocity 15rpm, mixing time 35min, whipping temp are 35 DEG C, the vacuum degree of vacuum condition is-
60kPa obtains the third mixed slurry that solid content is 58wt%；
(6) solvent deionized water is added into third mixed slurry and continues to stir under vacuum conditions, three axis planets stir
The revolution speed for mixing machine is 5rpm, rotational velocity 15rpm, mixing time 35min, and whipping temp is 35 DEG C, vacuum condition
Vacuum degree be -60kPa, obtain viscosity number be 8000mPas negative electrode slurry, the testing result of the negative electrode slurry such as 1 institute of table
Show.
In each step, the temperature of stirring is the constant temperature circulating by being passed through relevant temperature in three axis planetary mixer interlayers
The method of water controls.
Embodiment 4
(1) by negative electrode active material soft carbon and conductive agent electrically conductive graphite, thickener CMC powder according to mass ratio 94:2:1.5
It is added in three axis planetary mixers and is mixed, the revolution speed of three axis planetary mixers is 9rpm, and rotational velocity is
20rpm, mixing time 8min obtain the first mixed material；
(2) additive NMP is added into the first mixed material and stirs, the mass ratio of additive and the first mixed material is
3:100, the revolution speed of three axis planetary mixers are 12rpm, rotational velocity 35rpm, mixing time 18min, stirring temperature
Degree is 30 DEG C, obtains the second mixed material；
(3) solvent deionized water is added into the second mixed material and stirs under vacuum conditions, three axis planetary mixers
Revolution speed be 10rpm, rotational velocity 50rpm, mixing time 14min, whipping temp be 65 DEG C, vacuum condition it is true
Reciprocal of duty cycle is -50kPa, obtains the first mixed slurry that solid content is 84wt%；
(4) solvent deionized water is added into the first mixed slurry and continues to stir under vacuum conditions, three axis planets stir
The revolution speed for mixing machine is 18rpm, rotational velocity 65rpm, mixing time 45min, and whipping temp is 65 DEG C, vacuum condition
Vacuum degree be -50kPa, obtain solid content be 70wt% the second mixed slurry；
(5) binder SBR emulsion and solvent deionized water are added into the second mixed slurry and continues under vacuum conditions
The mass ratio of stirring, binder SBR emulsion and the first mixed material is 3:100, and the revolution speed of three axis planetary mixers is
15rpm, rotational velocity 30rpm, mixing time 28min, whipping temp are 28 DEG C, the vacuum degree of vacuum condition is-
50kPa obtains the third mixed slurry that solid content is 55wt%；
(6) solvent deionized water is added into third mixed slurry and continues to stir under vacuum conditions, three axis planets stir
The revolution speed for mixing machine is 9rpm, rotational velocity 25rpm, mixing time 28min, and whipping temp is 28 DEG C, vacuum condition
Vacuum degree be -50kPa, obtain viscosity number be 5000mPas negative electrode slurry, the testing result of the negative electrode slurry such as 1 institute of table
Show.
In each step, the temperature of stirring is the constant temperature circulating by being passed through relevant temperature in three axis planetary mixer interlayers
The method of water controls.
Embodiment 5
(1) negative electrode active material artificial graphite and natural graphite are pressed with the super conductive carbon of conductive agent, thickener CMC powder
It is added in three axis planetary mixers and is mixed according to mass ratio 60:34:2.5:1.7, the revolution speed of three axis planetary mixers
7rpm is spent, rotational velocity 27rpm, mixing time 7min obtain the first mixed material；
(2) additive ethyl alcohol is added into the first mixed material and stirs, the mass ratio of additive and the first mixed material
Revolution speed for 4.2:100, three axis planetary mixers is 11rpm, and rotational velocity 38rpm, mixing time 17min are stirred
Mixing temperature is 28 DEG C, obtains the second mixed material；
(3) solvent deionized water is added into the second mixed material and stirs under vacuum conditions, three axis planetary mixers
Revolution speed be 11rpm, rotational velocity 38rpm, mixing time 11min, whipping temp be 62 DEG C, vacuum condition it is true
Reciprocal of duty cycle is -30kPa, obtains the first mixed slurry that solid content is 87wt%；
(4) solvent deionized water is added into the first mixed slurry and continues to stir under vacuum conditions, three axis planets stir
The revolution speed for mixing machine is 17rpm, rotational velocity 63rpm, mixing time 57min, and whipping temp is 62 DEG C, vacuum condition
Vacuum degree be -30kPa, obtain solid content be 69wt% the second mixed slurry；
(5) binder SBR emulsion and solvent deionized water are added into the second mixed slurry and continues under vacuum conditions
The mass ratio of stirring, binder SBR emulsion and the first mixed material is 3.5:100, and the revolution speed of three axis planetary mixers is
17rpm, rotational velocity 48rpm, mixing time 27min, whipping temp are 28 DEG C, the vacuum degree of vacuum condition is-
30kPa obtains the third mixed slurry that solid content is 57wt%；
(6) solvent deionized water is added into third mixed slurry and continues to stir under vacuum conditions, three axis planets stir
The revolution speed for mixing machine is 11rpm, rotational velocity 38rpm, mixing time 28min, and whipping temp is 28 DEG C, vacuum condition
Vacuum degree be -30kPa, obtain viscosity number be 7000mPas negative electrode slurry, the testing result of the negative electrode slurry such as 1 institute of table
Show.
In each step, the temperature of stirring is the constant temperature circulating by being passed through relevant temperature in three axis planetary mixer interlayers
The method of water controls.
Comparative example 1
Slurry is prepared using wet process stirring technique, comprising the following steps:
Artificial graphite, super conductive carbon, CMC powder, SBR 96.5:1.0:1.0:1.5 in mass ratio preparation is spare, it stirs
Machine is mixed using double planetary mixer；
Double planetary mixer first is added in CMC powder and deionized water solvent, is vacuumized, rate of dispersion be 1000rpm,
180min to CMC is stirred under conditions of agitating paddle revolution speed is 25rpm, whipping temp is 25 DEG C to be completely dissolved, and CMC glue is made
Liquid；
Super conductive charcoal and SBR are added into CMC colloidal sol, vacuumizes, rate of dispersion is 1000rpm, agitating paddle revolves
Speed is 20rpm, whipping temp stirs 60min under conditions of being 25 DEG C, and black glue liquid is made；
Artificial graphite is added into black glue liquid, vacuumizes, rate of dispersion is 1200rpm, agitating paddle revolution speed is
25rpm, whipping temp stir 120min under conditions of being 25 DEG C, obtain uniform slurry；
The viscosity of above-mentioned resulting uniform sizing material is tested, if its viscosity is undesirable, adds a part of deionization
Aqueous solvent carries out slurry to adjust viscous, actual conditions are as follows: vacuumizes, rate of dispersion is 1000rpm, agitating paddle revolution speed is
20rpm, whipping temp stir 30min under conditions of being 25 DEG C, obtain the slurry that viscosity number is 6000mPa.s.
Comparative example 2
Slurry is prepared using dry stirring technique, comprising the following steps:
Artificial graphite, super conductive carbon, CMC powder and SBR 96.5:1.0:1.0:1.5 in mass ratio preparation is spare, it stirs
Machine is mixed using double planetary mixer；
Double planetary mixer first is added in artificial graphite, super conductive charcoal and CMC powder are then sequentially added, in dispersion speed
Degree is 800rpm, agitating paddle revolution speed is 10rpm, whipping temp stirs 10min under conditions of being 25 DEG C, and mixed powder is made
Material；
Deionized water solvent is added into mixed powder, vacuumizes, rate of dispersion be 1200rpm, agitating paddle revolution speed
Degree is 25rpm, whipping temp stirs 180min under conditions of being 25 DEG C, and the first mixed slurry is made；
SBR emulsion is added into the first mixed slurry, vacuumizes, is 1000rpm, agitating paddle revolution speed in rate of dispersion
30min is stirred under conditions of being 25 DEG C for 20rpm, whipping temp, obtains uniform slurry；
The viscosity of above-mentioned resulting uniform sizing material is tested, if its viscosity is undesirable, adds a part of deionization
Aqueous solvent carries out slurry to adjust viscous, actual conditions are as follows: vacuumizes, rate of dispersion is 1000rpm, agitating paddle revolution speed is
20rpm, whipping temp stir 30min under conditions of being 25 DEG C, obtain the slurry that viscosity number is 6000mPa.s.
Interpretation of result:
When carrying out granularity and standing sedimentation to the slurry of Examples 1 to 5, comparative example 1 and comparative example 2 under the same conditions
Between test, test result is as shown in table 1, as it can be seen from table 1 Examples 1 to 5 is resulting compared to documents 1 and 2
Slurry more evenly, the standing sedimentation time it is longer, stir slurry needed for the time it is also shorter.
2 slurry test result of 1 Examples 1 to 5 of table, comparative example 1 and comparative example
| The slurry agitation time | Pulp particle degree D50 | The slurry standing sedimentation time | |
| Embodiment 1 | 134min | 13.0μm | 132h |
| Embodiment 2 | 127min | 13.8μm | 130h |
| Embodiment 3 | 175min | 12.5μm | 132h |
| Embodiment 4 | 136min | 12.8μm | 130h |
| Embodiment 5 | 147min | 13.6μm | 135h |
| Comparative example 1 | 390min | 13μm | 80h |
| Comparative example 2 | 250min | 15μm | 96h |
The slurry of Examples 1 to 5, comparative example 1 and comparative example 2 is coated respectively under the same conditions dry to be made
Then pole piece tests the cohesive force (180 ° of peel tests) of collector in each pole piece and and carries out the survey of lithium battery resistance to each pole piece
Examination, test result is as shown in table 2, from table 2 it can be seen that in the resulting pole piece of Examples 1 to 5 the cohesive force of collector it is bigger,
Pole piece resistance is smaller.
2 pole piece test result of 2 Examples 1 to 5 of table, comparative example 1 and comparative example
| Collector cohesive force | Pole piece resistance | |
| Embodiment 1 | 13~15N/m | 0.08~0.15 Ω/100 μm |
| Embodiment 2 | 13~14N/m | 0.06~0.13 Ω/100 μm |
| Embodiment 3 | 14~16N/m | 0.08~0.14 Ω/100 μm |
| Embodiment 4 | 13~15N/m | 0.09~0.15 Ω/100 μm |
| Embodiment 5 | 12~14N/m | 0.06~0.12 Ω/100 μm |
| Comparative example 1 | 4~7N/m | 0.12~0.35 Ω/100 μm |
| Comparative example 2 | 4~8N/m | 0.10~0.30 Ω/100 μm |
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example
Point is included at least one embodiment or example of the invention.In the present specification, schematic expression of the above terms are not
It must be directed to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be in office
It can be combined in any suitable manner in one or more embodiment or examples.In addition, without conflicting with each other, the skill of this field
Art personnel can tie the feature of different embodiments or examples described in this specification and different embodiments or examples
It closes and combines.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, modifies, replacement and variant.
Claims (10)
1. a kind of method for preparing negative electrode slurry characterized by comprising
(1) negative electrode active material and conductive agent, thickener are added in three axis planetary mixers and are mixed, to obtain
First mixed material；
(2) additive is added in the first mixed material of Xiang Suoshu and stirs, to obtain the second mixed material；
(3) solvent is added in the second mixed material of Xiang Suoshu and stirs under vacuum conditions, is 80wt% to obtain solid content
The first mixed slurry of~90wt%；
(4) solvent is added in the first mixed slurry of Xiang Suoshu and continues to stir under vacuum conditions, to obtain solid content
For the second mixed slurry of 60wt%~72wt%；
(5) binder and the solvent are added in the second mixed slurry of Xiang Suoshu and continues to stir under vacuum conditions, so as to
The third mixed slurry for being 53wt%~58wt% to solid content；
(6) solvent is added in Xiang Suoshu third mixed slurry and continues to stir under vacuum conditions, to obtain viscosity number
For the negative electrode slurry of 3000~8000mPas.
2. the method according to claim 1, wherein in step (1), the revolution of the three axis planetary mixer
Speed is 5~10rpm, and rotational velocity is 15~30rpm, and mixing time is 5~10min；
It is optional, in step (1), the mass ratio of the negative electrode active material and the conductive agent, the thickener be (92~
98): (0.5~4): (0.5~2)；
Optional, in step (1), the negative electrode active material is in artificial graphite, natural graphite, hard carbon, soft carbon
At least one；
Optional, in step (1), the conductive agent is in super conductive carbon, carbon nanotube, graphene and electrically conductive graphite
At least one of；
Optionally, in step (1), the thickener is at least one of selection CMC powder, CMC solution.
3. the method according to claim 1, wherein in step (2), the revolution of the three axis planetary mixer
Speed is 5~15rpm, and rotational velocity is 15~45rpm, and mixing time is 10~20min, and whipping temp is 0 DEG C~40 DEG C；
Optional, in step (2), the additive is selected from least one of acetone, ethyl alcohol, 1,3-BDO, NMP；
Optional, in step (2), the mass ratio of the additive and first mixed material is (0.1~5): 100.
4. the method according to claim 1, wherein in step (3), the revolution of the three axis planetary mixer
Speed is 5~20rpm, and rotational velocity is 15~60rpm, and mixing time is 10~15min, and whipping temp is 55 DEG C~70 DEG C；
Optional, in step (3), the solvent is at least one of deionized water, NMP.
5. the method according to claim 1, wherein in step (4), the revolution of the three axis planetary mixer
Speed is 15~25rpm, and rotational velocity is 45~75rpm, and mixing time is 40~65min, and whipping temp is 55 DEG C~70 DEG C.
6. the method according to claim 1, wherein in step (5), the revolution of the three axis planetary mixer
Speed is 5~20rpm, and rotational velocity is 15~60rpm, and mixing time is 25~35min, and whipping temp is 20 DEG C~35 DEG C；
Optional, in step (5), the binder is selected from least one of SBR, LA132, LA133；
Optional, in step (5), the mass ratio of the binder and first mixed material is (1~5): 100.
7. the method according to claim 1, wherein in step (6), the revolution of the three axis planetary mixer
Speed is 5~15rpm, and rotational velocity is 15~45rpm, and mixing time is 25~35min, and whipping temp is 20 DEG C~35 DEG C.
8. the method according to claim 1, wherein in step (3), step (4), step (5), step (6),
The vacuum degree of the vacuum condition is separately -90~-30kPa.
9. a kind of negative electrode slurry, which is characterized in that the negative electrode slurry is using side according to any one of claims 1 to 8
What method was prepared.
10. a kind of lithium ion battery, which is characterized in that the cathode of the lithium ion battery is using as claimed in claim 9 negative
Pole slurry is prepared.
Priority Applications (1)
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| CN112201766A (en) * | 2020-09-30 | 2021-01-08 | 蜂巢能源科技有限公司 | Negative electrode slurry and preparation method and application thereof |
| CN112713257A (en) * | 2020-12-29 | 2021-04-27 | 湖北亿纬动力有限公司 | Preparation method of negative electrode slurry and negative electrode slurry |
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