CN106299250B - A kind of preparation method of electrode slurry - Google Patents
A kind of preparation method of electrode slurry Download PDFInfo
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- CN106299250B CN106299250B CN201610969325.XA CN201610969325A CN106299250B CN 106299250 B CN106299250 B CN 106299250B CN 201610969325 A CN201610969325 A CN 201610969325A CN 106299250 B CN106299250 B CN 106299250B
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F33/00—Other mixers; Mixing plants; Combinations of mixers
- B01F33/70—Mixers specially adapted for working at sub- or super-atmospheric pressure, e.g. combined with de-foaming
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The present invention relates to the preparation methods of electrode slurry, and the preparation method comprises the following steps: 1) the 1st particulate material, mixing being added into solvent；2) binder solution and/or thickener soln, mixing optionally, are added into step 1) acquired solution；3) into step 2) acquired solution, the 2nd particulate material, the (n-1)th particulate material is added in a manner of repeating step 1) and step 2)；4) the n-th particulate material is added into step 3) acquired solution, mixes；5) optionally, add thickener, mixing into step 4) acquired solution；6) be added adhesive into step 5) acquired solution, mixing to get.The uniformity of the electrode slurry that the present invention obtains, each constituent component dispersion obtains significant improve；Mixing time shortens, and improves production efficiency.The electrode slurry that method provided by the present invention obtains, is fabricated to pole piece, is assembled into lithium ion battery, the capacity performance of battery is sufficiently, consistency is high, has extended cycle life.
Description
Technical field
The invention belongs to battery technology fields, are related to a kind of preparation method of electrode slurry.
Background technique
In lithium ion battery manufacturing process, slurry mixed processes are a wherein important procedures.Li-ion electrode slurry
Material generally comprises positive and negative anodes active material, conductive agent, bonding agent.For properties such as the dispersibility, the stability that improve electrode slurry,
The additives such as stabilizer, dispersing agent or surfactant can also be added in slurry.In addition, in order to improve other property of battery
Can, other function additive, such as nano aluminium oxide can also be added in slurry.It is granulated activated in positive and negative electrode slurry
Substance, the dispersibility of conductive agent and functional additive and uniformity will affect lithium ion in the movement of two interpolar of battery,
Therefore the mixing dispersion of the slurry of each pole piece material is most important in lithium ion battery production.The quality of slurry dispersion quality,
To the capacity of battery plays, forthright, cyclicity and consistency have large effect again, subsequent lithium ion battery will have a direct impact on
The performance of the quality of production and products thereof.
During preparing electrode slurry, the mode for generalling use stirring is sufficiently mixed the various components in slurry
It is even, and there is certain viscosity, while showing preferable mobility.Wherein crucial problem is to keep various component mixing equal
It is even, followed by consider viscosity, mobility and solid content.
The agitating mode of electrode slurry mainly has dry stirring and wet process stirring at present.As shown in Figure 1, dry stirring is main
Be by each powder tentatively after mixing, add solvent and dispersing agent, realize the effect of dispersion.Dry mixed mixing speed
Comparatively fast, about 4-8 hours, but the uniformity stirred is poor.As shown in Fig. 2, wet process stirring is first glue, conductive agent is then added
Stirring adds major ingredient (i.e. active material) stirring.The used time of wet process stirring is longer, and generally higher than 8 hours, the uniformity of stirring
It is higher than dry stirring.
The dispersion effect of each component in different environments is different in electrode slurry.Nano-scale is usually used in conductive agent
Carbon black, such as Super P (agent of SP type carbon black conductive), acetylene black, KS series carbon particulate, carbon fiber, carbon nanotube (CNT), section
Qin is black etc..It is generally believed that the particle size due to nano particle is small, surface area is big, so the dispersibility of nano particle can phase
To poor.
CN104466111A discloses a kind of preparation process of lithium electrode slurry, and rubber powder, conductive agent, active material are distinguished
It is mixed and made into solution with solvent, then conductive agent solution, active substance solution and glue are mixed, finally plus residual solvent mixes.
CN101694872A and CN103022433A discloses a kind of production method of li-ion electrode slurry mixing, is
By conductive agent, active material it is dry-mixed after, then mix with binder solution.
Disperse each component in li-ion electrode slurry more uniform, to further improve lithium ion battery
Electrical property, this is that those skilled in the art endeavour always the technical issues of solving.
Summary of the invention
It is an object of the invention to realize the dispersion effect for for example improving electrode slurry, and/or shorten mixing time, and/
Or the one or more in the electrical property of improvement battery, specifically, for example, the normal capacity for playing battery, and/or extension follow
The ring service life, and/or improve consistency.
Inventor has carried out a large amount of experiment to realize above-mentioned one or more purpose, it has unexpectedly been found that, use is wet
Method stirring, be conducive to little particle dispersion in the environment of, the preferential lesser particle of dispersion particle diameter, then again with partial size biggish
Grain mixing, can be such that partial size larger particles are uniformly mixed with partial size smaller particle, reach better dispersion effect in this way.By this hair
The electrode slurry that the preparation method of bright offer obtains is uniformly dispersed, and is fabricated to pole piece, is assembled into lithium ion battery, battery performance obtains
To improvement.
It include particulate material in the electrode slurry in particular it relates to a kind of preparation method of electrode slurry,
The particulate material includes the 1st particulate material, the 2nd particulate material ... ..., the (n-1)th particulate material and the n-th particle
Shape substance, wherein n is natural number more than or equal to 3, and the sequence of the granularity of the particulate material from small to large are as follows: the 1st
Particulate material < the 2nd particulate material < ... the < the (n-1)th particulate material < the n-th particulate material,
The preparation method comprises the following steps:
1) the 1st particulate material, mixing are added into solvent；
2) binder solution and/or thickener soln, mixing optionally, are added into step 1) acquired solution；
3) into step 2) acquired solution, the 2nd granular substance is added in a manner of repeating step 1) and step 2)
Matter ..., the (n-1)th particulate material；
4) the n-th particulate material is added into step 3) acquired solution, mixes；
5) optionally, add thickener, mixing into step 4) acquired solution；
6) adhesive is added into step 5) acquired solution, mixes, obtains electrode slurry.
In a preferred embodiment, the preparation method of electrode slurry of the present invention, wherein the particle
Shape substance includes active material (preferably lithium ion battery active material, such as positive active material, including cobalt acid lithium, ternary
Material, LiMn2O4 or negative electrode active material, including artificial graphite, composite graphite, natural graphite, Si-C composite material),
Optionally, the particulate material further includes that (conductive agent is selected from Super P (SP type charcoal unlicensed tour guide to conductive agent
Electric agent), acetylene black, KS series carbon particulate, carbon fiber, carbon nanotube (CNT), Ketjen black) or/and functional additive (such as
Nano aluminium oxide).
In a preferred embodiment, the preparation method of the aforementioned described in any item electrode slurrys of the present invention, wherein
The solvent is water or N-Methyl pyrrolidone.
In a preferred embodiment, the preparation method of the aforementioned described in any item electrode slurrys of the present invention, wherein
Described adhesive solution be polyvinylidene fluoride (homopolymer, copolymer or its modifier including vinylidene), polyacrylic acid,
The mixture of sodium alginate or butadiene-styrene rubber and the solvent.
In a preferred embodiment, the preparation method of the aforementioned described in any item electrode slurrys of the present invention, wherein
The thickener soln is the mixture of hydroxymethyl cellulose and solvent.
In a preferred embodiment, the preparation method of the aforementioned described in any item electrode slurrys of the present invention, wherein
The binder solution and/or thickener soln that step 2) is added are that whole adhesive needed for electrode slurry and/or thickener are molten
Liquid 0~40% (preferably 1-40%, further preferably 10-30%, such as 20%),
The thickener that step 5) is added is remaining thickener,
The adhesive that step 6) is added is remaining adhesive.
In a preferred embodiment, the preparation method of the aforementioned described in any item electrode slurrys of the present invention, wherein
The natural number that the n is 3~6, preferably 3,4,5 or 6.
In a preferred embodiment, the preparation method of the aforementioned described in any item electrode slurrys of the present invention, it is described
Electrode slurry is anode sizing agent, in which: the particulate material includes conductive agent and positive active material, and the solvent is
N-Methyl pyrrolidone, the binder solution be polyvinylidene fluoride (homopolymer, copolymer including vinylidene or its
Modifier) and the solvent mixture.
In a preferred embodiment, the preparation method of the aforementioned described in any item electrode slurrys of the present invention, it is described
Electrode slurry is anode sizing agent, in which: the 3, the 1st particulate material of n be carbon black conductive agent (such as SP type carbon black conductive agent), the 2nd
Particulate material is graphite agent (such as KS-6 type graphite agent), and the 3rd particulate material is positive active material.
In a preferred embodiment, the preparation method of the aforementioned described in any item electrode slurrys of the present invention, it is described
Electrode slurry is anode sizing agent, and the preparation method comprises the following steps:
1) the 1st particulate material, mixing are added into the solvent；
2) the 2nd particulate material, mixing are added into step 1) acquired solution；
3) binder solution optionally, is added into step 2) acquired solution (to be preferably added to needed for electrode slurry all glue
0~40% (preferably 1-40%, further preferably 10-30%, such as 20%)) of mixture solution, mixing；
4) the 3rd particulate material, mixing are added into step 3) acquired solution；
5) be added adhesive into step 4) acquired solution, mixing to get.
In a preferred embodiment, the preparation method of the aforementioned described in any item electrode slurrys of the present invention, it is described
Electrode slurry is negative electrode slurry, in which: the particulate material includes conductive agent and negative electrode active material, and the solvent is
Water, the thickener soln are the mixture of hydroxymethyl cellulose and the solvent, and the binder solution is butylbenzene rubber
The mixture of glue and the solvent.
In a preferred embodiment, the preparation method of the aforementioned described in any item electrode slurrys of the present invention, it is described
Electrode slurry is negative electrode slurry, in which: the 3, the 1st particulate material of n be carbon black conductive agent (such as SP type carbon black conductive agent), the 2nd
Particulate material is graphite agent (such as KS-6 type graphite agent), and the 3rd particulate material is negative electrode active material.
In a preferred embodiment, the preparation method of the aforementioned described in any item electrode slurrys of the present invention, it is described
Electrode slurry is negative electrode slurry, and the preparation method comprises the following steps:
1) the 1st particulate material, mixing are added into the solvent；
2) the 2nd particulate material, mixing are added into step 1) acquired solution；
3) thickener soln optionally, is added into step 2) acquired solution (to be preferably added to needed for electrode slurry all increase
0~40% (preferably 1-40%, further preferably 10-30%, such as 20%)) of thick agent solution, mixing；
4) the 3rd particulate material, mixing are added into step 3) acquired solution；
5) thickener is added into step 4) acquired solution, mixes；
6) be added adhesive into step 5) acquired solution, mixing to get.
In a preferred embodiment, the preparation method of the aforementioned described in any item electrode slurrys of the present invention, wherein
Mixed mode is stirring.
In a preferred embodiment, the preparation method of the aforementioned described in any item electrode slurrys of the present invention, wherein
The binder solution and/or thickener is prepared by following preparation method: described adhesive and/or thickener are added
It is mixed into the solvent.Preferably, described adhesive and/or thickener are added in batches in the solvent, each batch
Mixed after addition, add next batch mixing, until whole adhesives and/or thickener add and mix to get.
In a preferred embodiment, during preparing binder solution, described adhesive point 1 batch to m batches adds
Enter into solvent, the 3,4 or 5, the 1st batch of additional amount of m is about the half of the total additional amount of adhesive, and m-1 batches of additional amounts are about surplus
The half of remaining adhesive, m batches are added remaining adhesive.
In a preferred embodiment, during preparing binder solution, described adhesive is added in solvent
Afterwards, mixed method are as follows: after every batch of adhesive is added, first once stirred, using revolution 10-25r/min (such as 20r/
Min), the parameter atmospheric agitation of rotation 600-1000r/min (such as 800r/min), mixing time be 10-30min (such as
20min)；Carry out secondary agitation again, using revolution 20-35r/min (such as 30r/min), rotation 1500-3000r/min (such as
2000r/min or 2500r/min) parameter be stirred under vacuum, mixing time be 40-150min (such as 60min or 120min).It stirs
It mixes number and the visual mixed effect of mixing time and increases or decreases.Preferably, stirring is 20-60 DEG C (such as 45 DEG C) in temperature
Lower progress.
In a preferred embodiment, during preparing thickener soln, the thickener point 1 batch to m batches adds
Enter into solvent, the 3,4 or 5, the 1st batch of additional amount of m is about the half of the total additional amount of thickener, and m-1 batches of additional amounts are about surplus
The half of remaining thickener, m batches are added remaining thickener.
In a preferred embodiment, during preparing thickener soln, the thickener is added to described molten
After in agent, mixed method are as follows: after every batch of thickener soln is added, first once stirred, using revolution 5-20r/min (example
Such as 10r/min or 18r/min), the parameter atmospheric agitation of rotation 400-1000r/min (such as 500r/min or 800r/min),
Mixing time is 5-20min (such as 10min)；Carry out secondary agitation again, using revolution 15-20r/min (such as 18r/min),
The parameter atmospheric agitation of rotation 700-1000r/min (such as 800r/min), mixing time are 15-30min (such as 20min)；
Then carry out triple mixing again, using revolution 20-35r/min (such as 25r/min), rotation 1300-2500r/min (such as
1500r/min or 2000r/min) parameter be stirred under vacuum, mixing time be 30-150min (such as 60min or 120min).Often
Pressure stirs number and the visual mixed effect of mixing time and increases or decreases.Preferably, stirring temperature be 20-60 DEG C (such as
45 DEG C) under carry out.
In a preferred embodiment, the preparation method of the aforementioned described in any item electrode slurrys of the present invention, the 1st
After particulate matter is added, mixed method are as follows: first once stirred, using revolution 5-30r/min (such as 20r/min), certainly
Turn the parameter atmospheric agitation of 200-1500r/min (such as 400r/min, 800r/min or 1200r/min), mixing time 5-
20min (such as 10min)；Secondary agitation is carried out again, using revolution 15-35r/min (such as 25r/min or 30r/min), rotation
The parameter of 1200-2000r/min (such as 1500r/min) is stirred under vacuum, mixing time be 20-60min (such as 30min or
40min)；Atmospheric agitation number and the visual mixed effect of mixing time and increase or decrease；Preferably, stirring temperature be 20~
It is carried out under 30 DEG C (such as 25 DEG C).
In a preferred embodiment, the preparation method of the aforementioned described in any item electrode slurrys of the present invention, the 2nd
After particulate matter is added, mixed method are as follows: first once stirred, using revolution 5-30r/min (such as 20r/min), certainly
Turn the parameter atmospheric agitation of 200-1500r/min (such as 400r/min, 800r/min or 1200r/min), mixing time 5-
20min (such as 10min)；Secondary agitation is carried out again, using revolution 15-35r/min (such as 25r/min or 30r/min), rotation
The parameter of 1200-2000r/min (such as 1500r/min) is stirred under vacuum, mixing time be 20-60min (such as 30min or
40min)；Atmospheric agitation number and the visual mixed effect of mixing time and increase or decrease；Preferably, stirring temperature be 20~
It is carried out under 30 DEG C (such as 25 DEG C).
In a preferred embodiment, the preparation method of the aforementioned described in any item electrode slurrys of the present invention, the 3rd
Particulate matter point 1 batch to m batches is added in solution, and the 1st batch of additional amount is about the half of the 3rd total additional amount of particulate material, the
M-1 batches of additional amounts are about the half of remaining 3rd particulate material, and m batches are added remaining 3rd particulate material.Wherein m is 3,4
Or 5.
In a preferred embodiment, the preparation method of the aforementioned described in any item electrode slurrys of the present invention, it is each
After batch the 3rd particulate material is added, mixed method are as follows: first once stirred, using revolution 5-25r/min (such as 15r/
Min or 20r/min), the parameter atmospheric agitation of rotation 400-1200r/min (such as 500r/min or 800r/min), when stirring
Between be 5-20min (such as 10min)；Secondary agitation is carried out again, using revolution 15-25r/min (such as 20r/min), rotation
The parameter atmospheric agitation of 800-2000r/min (such as 1000r/min or 1500r/min), mixing time be 15-30min (such as
10min or 20min)；Then triple mixing is carried out again, using revolution 15-35r/min (such as 20r/min or 30r/min), certainly
Turn 1300-2500r/min (such as 1500r/min) parameter be stirred under vacuum, mixing time be 90-150min (such as
120min).Atmospheric agitation number and the visual mixed effect of mixing time and increase or decrease.Preferably, stirring is 20 in temperature
It is carried out under~30 DEG C (such as 25 DEG C).
In a preferred embodiment, the preparation method of the aforementioned described in any item electrode slurrys of the present invention, it is described
Binder solution be added after, mixed method are as follows: first once stirred, using revolution 5-20r/min (such as 15r/min),
The parameter atmospheric agitation of rotation 600-1200r/min (such as 800r/min), mixing time are 5-20min (such as 10min)；Again
Secondary agitation is carried out, using revolution 20-35r/min (such as 30r/min), rotation 800-2000r/min (such as 1000r/min
Or 1500r/min) parameter atmospheric agitation, mixing time be 15-30min (such as 20min)；Then triple mixing is carried out again,
It is stirred using the parameter vacuum of revolution 15-35r/min (such as 30r/min), rotation 2000-3000r/min (such as 2500r/min)
It mixes, mixing time is 90-150min (such as 120min).Atmospheric agitation number and the visual mixed effect of mixing time and increase or
It reduces.Preferably, stirring is carried out in the case where temperature is 20~30 DEG C (such as 25 DEG C).
In a preferred embodiment, the preparation method of the aforementioned described in any item electrode slurrys of the present invention, it is described
Thickener soln be added after, mixed method are as follows: first once stirred, using revolution 5-25r/min (such as 20r/min),
The parameter atmospheric agitation of rotation 600-1200r/min (such as 800r/min), mixing time are 5-20min (such as 10min)；Again
Secondary agitation is carried out, using revolution 20-35r/min (such as 30r/min), rotation 2000-3500r/min (such as 2500r/
Min parameter) is stirred under vacuum, and mixing time is 20-150min (such as 30min or 120min).Atmospheric agitation number and stirring
Time visual mixed effect and increase or decrease.Preferably, stirring is carried out in the case where temperature is 20~30 DEG C (such as 25 DEG C).
In a preferred embodiment, the preparation method of the aforementioned described in any item electrode slurrys of the present invention, wherein
The vacuum refers to vacuum degree≤- 0.08MPa environment.
The invention further relates to a kind of electrode slurrys, by the preparation method system of the aforementioned described in any item electrode slurrys of the present invention
It is standby to obtain.
The invention further relates to a kind of electrode plates, surface is coated with electrode slurry of the present invention.
The invention further relates to a kind of batteries, wherein including electrode plates of the present invention.
Heretofore described battery, preferably secondary cell, further preferably lithium ion battery.
In the present invention, the electrode slurry includes negative electrode slurry and anode sizing agent.
In the present invention, adhesive used in anode sizing agent is not limited to PVDF, any material that can be used as positive electrode binder
Material is suitable for the invention preparation method.
In the present invention, thickener agent used in negative electrode slurry is not limited to CMC, and any material that can be used as thickener is equal
It is suitable for the invention preparation method.
In the present invention, " granularity " indicates the mean size of particulate material.In one embodiment, institute of the present invention
" granularity " use " D50 " characterization stated, D50 are also meso-position radius or median particle diameter, and meaning is the cumulative particle sizes distribution an of sample
Percentage reaches partial size corresponding when 50%.Its physical significance is that partial size is greater than its particle and accounts for 50%, less than its
Grain also accounts for 50%.
Beneficial effects of the present invention:
The present invention optimizes slurry agitation technique by optimization charging sequence, can obtain having for following one or more
Beneficial effect:
1, the uniformity of each constituent component dispersion of slurry obtains significant improve；
2, mixing time shortens, and improves production efficiency；
3, the electrode slurry that method provided by the present invention obtains, is fabricated to pole piece, is assembled into lithium ion battery, battery
Capacity performance is sufficiently, consistency is high, has extended cycle life.
Detailed description of the invention
Dry powder stirs flow diagram to Fig. 1 in the prior art；
Fig. 2 wet process in the prior art stirs flow diagram；
Wet process Fig. 3 of the invention stirs flow diagram；
The anode pole piece scanning electron microscope (SEM) photograph for the anode sizing agent coating that Fig. 4 is obtained by embodiment 1；
The anode pole piece scanning electron microscope (SEM) photograph for the anode sizing agent coating that Fig. 5 is obtained by comparative example 1；
The cathode pole piece scanning electron microscope (SEM) photograph for the anode sizing agent coating that Fig. 6 is obtained by embodiment 1；
The cathode pole piece scanning electron microscope (SEM) photograph for the anode sizing agent coating that Fig. 7 is obtained by comparative example 1；
The cyclic curve of the soft-package battery for the electrode slurry assembling that Fig. 8 is obtained by embodiment 1 and comparative example 1.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and should not be taken as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
It can be with conventional products that are commercially available.
In following example, finely ground particle substance of the present invention is conductive agent, such as the agent of SP type carbon black conductive, SK-6 type stone
Black conductive agent；The large particulate matter is active material, such as artificial graphite, cobalt acid lithium.
As shown in figure 3, in an embodiment of the invention, it is of the invention the preparation method comprises the following steps: simultaneously prepare glue and
After the completion of conductive agent solution preparation active material is first added portionwise, after mixing, then in batches in conductive agent solution thereto
Glue is added, is uniformly mixed, is uniformly mixed if there is binder is added again, obtains positive and negative electrode glue.
In following example or experimental example, if percentage sign " % " is weight percent without specified otherwise.
If " vacuum " described in following example refers to vacuum degree≤- 0.08MPa environment without specified otherwise.
In following example or experimental example, stirring equipment used is vacuum mixer (30L, the red cloud mixing in Guangzhou
Equipment Co., Ltd)
" viscosity " can be using universal test canonical measure in industry in the present invention.For example, following example or experimental example
In, the viscosity of electrode slurry obtained is measured using the viscosmeter (U.S. Brookfield) of model LVDV-C.
In following example, solid content is the weight percent of total slurry shared by solid in solution.
Embodiment 1
1. the preparation of anode sizing agent
The formula of anode sizing agent is shown in Table 1.
Table 1
1) positive electrode binder solution is prepared
The solid content of positive electrode binder solution is that 10%, PVDF is added in two portions in solvent NMP, stirring technique and effect
As shown in table 2, whipping temp is 45 DEG C, the used time about 4 hours, obtains positive electrode binder solution.
Table 2
2) conductive agent solution is prepared
The preparation of conductive agent solution and the preparation of positive electrode binder solution carry out simultaneously substantially.By conductive agent and solvent NMP
It is stirred after mixing.Solvent NMP is weighed first, is added in agitated kettle, then conductive agent is added in two portions, and SP is added for the first time
Type carbon black conductive agent, second of addition KS-6 type graphite agent, stirring technique and effect are shown in Table 3, and whipping temp is 25 DEG C, is used
When about 1.5 hours, obtain conductive agent solution.
Table 3
3) active material and binder solution are added into conductive agent solution
Active material LCO is added in three times in conductive agent solution, after mixing evenly, adds binder solution, into
The last stirring of row.Specific stirring technique is shown in Table 4, and whipping temp is 25 DEG C.Wherein, after active material is all added, total
Mixing time is about 2.5 hours.At this point, positive electrode binder solution just stirs completion.Then glue is added, it is small to be stirred for about 3
When, slurry agitation is completed.Slurry agitation total used time is about 7 hours.
Table 4
After the completion of stirring, the anode sizing agent that solid content is 70% is obtained, slurry fluidity is good, agglomerating existing without obvious particle
As measuring viscosity is 5400Cp.
2. the preparation of negative electrode slurry
The formula of negative electrode slurry is as shown in table 5.
Table 5
1) cathode thickener soln is prepared
The concentration of cathode thickener soln is that 3%, CMC is added in two portions, and stirring technique is as shown in table 6, and whipping temp is
45 DEG C, the used time about 3.5 hours, obtain cathode thickener soln.
Table 6
2) conductive agent solution is prepared
The preparation of conductive agent solution and the preparation of cathode thickener soln carry out simultaneously substantially, and conduction is equally added in two portions
Agent, solvent are water, and the carbon black conductive agent of SP type, second of addition KS-6 type graphite agent, stirring technique and effect are added for the first time
Fruit is shown in Table 7, whipping temp be 25 DEG C the used time about 1 hour, obtain conductive agent solution.
Table 7
3) active material and cathode thickener soln are added into conductive agent solution
After the completion of conductive agent solution stirring, active material is added in conductive agent solution in three times, after mixing evenly, finally
Cathode thickener soln is added, is mixed, stirring technique is as shown in table 8, and whipping temp is 25 DEG C.Artificial graphite stirring is completed
Used time about 2.5 hours, in addition the mixing time (about 1 hour) of conductive agent solution, about 3.5 hours when sharing, at this point, glue is just
Stirring is completed.Then the amount for weighing required glue is added in two portions in the solution containing conductive agent and active material, is stirred
It mixes, the used time about 3 hours.Finally plus concentration is 45% SBR aqueous solution, continues to stir, the used time about 1.5 hours.
Table 8
After the completion of stirring, total used time about 8 hours, the negative electrode slurry that solid content is 43% is obtained, slurry fluidity is good, measures
Viscosity is 4000Cp.
Adhesive used in pole slurry in this implementation is not limited to PVDF, any material that can be used as positive electrode binder
It is suitable for the invention preparation method.Thickener agent used in negative electrode slurry is not limited to CMC, any to can be used as thickener
Material be suitable for the invention preparation method.
Embodiment 2
In the preparation method of heretofore described electrode slurry, can also conductive agent solution prepare after the completion of, first plus
Enter the binder solution or thickener soln of 10-60%, after mixing evenly, then active material and remaining bonding is added in batches
Agent solution or thickener soln.
30% binder solution is first added, specifically in the preparation of anode sizing agent in the present embodiment in conductive agent solution
Stirring technique is shown in Table 9, and whipping temp is 25 DEG C, and after mixing evenly, then active material and remaining binder solution is added in batch.
The preparation method is the same as that of Example 1 for binder solution, and the Adding Way and stirring technique of active material and remaining binder solution are same
Embodiment 1.
Table 9
In embodiment 2, in electrode slurry preparation process, some adhesive solution is first added in conductive agent solution, makes
Conductive agent solution has certain viscosity, therefore can carry out the higher dispersion for stirring speed, equally can get uniform dispersion effect.
Comparative example 1
As shown in Fig. 2, carrying out slurry agitation, the same embodiment of the formula of anode and cathode slurry using traditional wet process stirring means
1。
The stirring technique of anode sizing agent is shown in Table 10, and total used time about 11.5 hours, whipping temp whole process was 25 DEG C.Stirring is completed
Afterwards, anode sizing agent, slurry viscosity 6300Cp are obtained.
Table 10
The stirring technique of negative electrode slurry is shown in Table 11, and the used time about 10 hours, whipping temp whole process was 25 DEG C.After the completion of stirring,
Obtain negative electrode slurry, slurry viscosity 4000Cp.
Table 11
The dispersion effect of the different preparation methods of experimental example 1
It after the completion of the positive and negative electrode slurry agitation that embodiment 1 and comparative example 1 are obtained, is sieved, is coated with, obtained positive and negative
Pole pole piece.Electronic Speculum observation is scanned to positive and negative plate, investigates the effect of slurry agitation.Electronic Speculum model FEI
Quanta650F。
It can be observed by Fig. 4 to Fig. 7, using preparation method and traditional preparation methods slurry obtained of the invention, divide
After not being coated, uniformity has marked difference, and specific comparing result is shown in Table 12.
Table 12
2 electrical property experiment of experimental example
In order to further verify the advantage of preparation method provided by the invention, embodiment 1 and comparative example 1 are obtained respectively
Positive and negative electrode slurry is coated respectively and is made pole piece, by the pole piece of acquisition carry out roll-in, slitting, film-making, winding, top side seal,
After vacuum drying, fluid injection, an envelope, chemical conversion, fixture baking, two envelopes, it is assembled into soft-package battery, specific technological parameter and equipment
Model is shown in Table 13.Vacuum drying, fluid injection, fixture baking are all made of conventional method in that art progress.
Table 13 prepares the technological parameter and equipment of soft-package battery
Volume test and cycle performance test are carried out to made soft-package battery.
The method of volume test are as follows: 2000mA constant-current constant-voltage charging to 4.35V, cut-off current 200mA；After standing 10min,
2000mA constant-current discharge stands 10min to 3.0V.Circulation is 3 times above, takes the discharge capacity of last time for the capacity of battery.
The result of volume test is as shown in table 14, using the battery for the assembled acquisition of electrode slurry that comparative example 1 obtains, holds
Measure average out to 4170mAh, gram specific capacity average out to 155.5mAh/g of cobalt acid lithium.The electrode obtained using the embodiment of the present invention 1
The battery of the assembled acquisition of slurry, capacity average out to 4236.3mAh, corresponding gram of specific capacity is 158.2mAh/g.As it can be seen that this hair
The electrode slurry that the preparation method of bright offer obtains can make the volumetric properties of battery get a promotion.
14 volume test result of table
The test method of cycle performance are as follows: 2000mA constant-current constant-voltage charging to 4.35V, cut-off current 200mA；It stands
After 10min, 2000mA constant-current discharge to 3.0V stands 10min.It is lasting to carry out the above circulation.Loop test result is shown in Fig. 8, adopts
With circulating battery 155 times of the electrode slurry assembling that comparative example 1 obtains, the electrode slurry assembling that is obtained using embodiment 1
Circulating battery 160 times.
As seen from Figure 8, the cycle performance for the battery being assembled into using the electrode slurry that embodiment 1 obtains is apparently higher than use
The cycle performance for the battery that the electrode slurry that comparative example 1 obtains is assembled into.They hold in 50 times, 100 times and 150 times circulations
Amount conservation rate correlation data is shown in Table 15.
The partial results of 15 cycle performance of table test
Although a specific embodiment of the invention has obtained detailed description, it will be understood to those of skill in the art that root
According to all introductions having disclosed, those details can be carry out various modifications and be replaced, these change in guarantor of the invention
Within the scope of shield.Full scope of the invention is given by the appended claims and any equivalents thereof.
Claims (35)
- It include particulate material in the electrode slurry 1. a kind of preparation method of electrode slurry, the particulate material includes 1st particulate material, the 2nd particulate material ... ..., the (n-1)th particulate material and the n-th particulate material, wherein n be greater than Or the natural number equal to 3, and the sequence of the granularity of the particulate material from small to large are as follows: the 1st particulate material < the 2nd particle Shape substance < ... the < the (n-1)th particulate material < the n-th particulate material,The preparation method comprises the following steps:1) the 1st particulate material, mixing are added into solvent；2) binder solution and/or thickener soln, mixing are added into step 1) acquired solution；3) into step 2) acquired solution, be added in a manner of repeating step 1) and step 2) the 2nd particulate material ..., the N-1 particulate material；4) the n-th particulate material is added into step 3) acquired solution, mixes；5) add thickener, mixing into step 4) acquired solution；6) adhesive is added into step 5) acquired solution, mixes, obtains electrode slurry.
- 2. preparation method described in claim 1, the particulate material includes active material.
- 3. preparation method as claimed in claim 2, the particulate material further includes conductive agent or/and functional additive.
- 4. preparation method as claimed in claim 2, wherein the active material is lithium ion battery active material.
- 5. preparation method as claimed in claim 4, wherein the lithium ion battery active material is positive active material or bears Pole active material.
- 6. preparation method described in claim 5, wherein the positive active material includes cobalt acid lithium, ternary material or mangaic acid Lithium.
- 7. preparation method described in claim 5, wherein the negative electrode active material includes artificial graphite, composite graphite, day Right graphite or Si-C composite material.
- 8. preparation method as claimed in claim 3, wherein the conductive agent is selected from Super P (agent of SP type carbon black conductive), acetylene Black, the serial carbon particulate of KS, carbon fiber and carbon nanotube (CNT), Ketjen black.
- 9. preparation method as claimed in claim 3, wherein the functional additive is nano aluminium oxide.
- 10. the described in any item preparation methods of claim 1 to 9, wherein the solvent is water or N-Methyl pyrrolidone.
- 11. the described in any item preparation methods of claim 1 to 9, wherein described adhesive solution is polyvinylidene fluoride, poly- third The mixture of olefin(e) acid, sodium alginate or butadiene-styrene rubber and the solvent.
- 12. preparation method described in claim 11, wherein the polyvinylidene fluoride includes the homopolymer of vinylidene, is total to Polymers or its modifier.
- 13. preparation method described in any one of claim 1 to 9,12, wherein the thickener soln is hydroxymethyl cellulose With the mixture of solvent.
- 14. preparation method described in any one of claim 1 to 9,12, binder solution that wherein step 2) is added and/ Or thickener soln is the 0~40% of whole adhesive needed for electrode slurry and/or thickener soln.
- 15. preparation method described in claim 14, the binder solution and/or thickener soln that wherein step 2) is added are The 1-40% of whole adhesive and/or thickener soln needed for electrode slurry.
- 16. preparation method described in claim 15, the binder solution and/or thickener soln that wherein step 2) is added are The 10-30% of whole adhesive and/or thickener soln needed for electrode slurry.
- 17. preparation method described in claim 16, the binder solution and/or thickener soln that wherein step 2) is added are 20% of whole adhesive and/or thickener soln needed for electrode slurry.
- 18. preparation method described in any one of claim 1 to 9,12,15 to 17, wherein the natural number that the n is 3~6.
- 19. preparation method described in claim 18, wherein the n is 3,4,5 or 6.
- 20. preparation method described in any one of claim 1-9,12,15 to 17,19, in which: the electrode slurry is anode Slurry, the particulate material include conductive agent and positive active material, and the solvent is N-Methyl pyrrolidone, the bonding Agent solution is the mixture of polyvinylidene fluoride and the solvent.
- 21. preparation method described in claim 20, in which: the 3, the 1st particulate material of n is carbon black conductive agent, the 2nd graininess Substance is graphite agent, and the 3rd particulate material is positive active material.
- 22. preparation method described in claim 21, in which: carbon black conductive agent is the carbon black conductive agent of SP type.
- 23. preparation method described in claim 21, in which: graphite agent is the graphite agent of KS-6 type.
- 24. the described in any item preparation methods of claim 21 to 23, comprising the following steps:1) the 1st particulate material, mixing are added into the solvent；2) the 2nd particulate material, mixing are added into step 1) acquired solution；3) binder solution is added into step 2) acquired solution, mixes；4) the 3rd particulate material, mixing are added into step 3) acquired solution；5) be added adhesive into step 4) acquired solution, mixing to get.
- 25. preparation method described in any one of claim 1-9,12,15 to 17,19, in which: the electrode slurry is cathode Slurry, the particulate material include conductive agent and negative electrode active material, and the solvent is water, and the thickener soln is hydroxyl first The mixture of base cellulose and the solvent, described adhesive solution are the mixture of butadiene-styrene rubber and the solvent.
- 26. preparation method described in claim 25, in which: the 3, the 1st particulate material of n is carbon black conductive agent, the 2nd graininess Substance is graphite agent, and the 3rd particulate material is negative electrode active material.
- 27. preparation method described in claim 26, in which: carbon black conductive agent is the carbon black conductive agent of SP type.
- 28. preparation method described in claim 26, in which: graphite agent is the graphite agent of KS-6 type.
- 29. the described in any item preparation methods of claim 26 to 28, comprising the following steps:1) the 1st particulate material, mixing are added into the solvent；2) the 2nd particulate material, mixing are added into step 1) acquired solution；3) thickener soln is added into step 2) acquired solution, mixes；4) the 3rd particulate material, mixing are added into step 3) acquired solution；5) thickener is added into step 4) acquired solution, mixes；6) be added adhesive into step 5) acquired solution, mixing to get.
- 30. preparation method described in any one of claim 1 to 9,12,15 to 17,19,21 to 23,26 to 28, wherein mixing Mode be stirring.
- 31. preparation method described in any one of claim 1 to 9,12,15 to 17,19,21 to 23,26 to 28, wherein described Binder solution and/or thickener are prepared by following preparation method: described adhesive and/or thickener being added to described It is mixed in solvent.
- 32. preparation method described in claim 31, wherein described adhesive solution and/or thickener are by following preparation method system It is standby to obtain:Described adhesive and/or thickener are added in batches in the solvent, and each batch mixes after being added, and are added next Batch mixing, until whole adhesives and/or thickener add and mix to get.
- 33. a kind of electrode slurry is prepared by the described in any item preparation methods of claims 1 to 32.
- 34. a kind of electrode plates, surface is coated with electrode slurry described in claim 33.
- 35. a kind of battery, wherein including electrode plates described in claim 34.
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| CN108428865A (en) * | 2018-03-05 | 2018-08-21 | 天臣新能源研究南京有限公司 | A kind of preparation method of lithium ion battery anode slurry |
| CN109378468B (en) * | 2018-11-28 | 2020-10-30 | 邓丽萍 | Pulping method of ternary material for lithium ion battery |
| CN109758960B (en) * | 2019-03-07 | 2020-09-29 | 广东宏工物料自动化系统有限公司 | Lithium ion battery positive and negative electrode slurry mixing production system and slurry preparation process |
| CN111081970B (en) * | 2019-12-25 | 2021-02-05 | 江西安驰新能源科技有限公司 | Slurry mixing process for improving solid content of slurry |
| CN111725508A (en) * | 2020-06-22 | 2020-09-29 | 湖北亿纬动力有限公司 | Preparation method of negative electrode slurry without glue solution, obtained negative electrode slurry and application |
| CN114628648A (en) * | 2021-07-08 | 2022-06-14 | 万向一二三股份公司 | High-performance silicon-carbon negative electrode piece and preparation method thereof |
| CN114628662B (en) * | 2021-10-08 | 2023-10-03 | 万向一二三股份公司 | Preparation method for improving solid content of lithium battery positive electrode slurry |
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