CN106299250A - A kind of preparation method of electrode slurry - Google Patents
A kind of preparation method of electrode slurry Download PDFInfo
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- CN106299250A CN106299250A CN201610969325.XA CN201610969325A CN106299250A CN 106299250 A CN106299250 A CN 106299250A CN 201610969325 A CN201610969325 A CN 201610969325A CN 106299250 A CN106299250 A CN 106299250A
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- particulate material
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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
-
- 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
Abstract
The present invention relates to the preparation method of electrode slurry, described preparation method comprises the following steps: 1) add the 1st particulate material, mixing in solvent；2) alternatively, to step 1) gained solution adds binder solution and/or thickener soln, mixing；3) to step 2) in gained solution, to repeat step 1) and step 2) in the way of add the 2nd particulate material, the n-th 1 particulate materials；4) to step 3) gained solution adds the n-th particulate material, mixing；5) alternatively, to step 4) gained solution adds thickening agent, mixing；6) to step 5) gained solution adds binding agent, mixing, to obtain final product.The electrode slurry that the present invention obtains, each composition scattered uniformity of component obtains significantly to be improved；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, and the capacity of battery plays fully, concordance is high, have extended cycle life.
Description
Technical field
The invention belongs to cell art, relate to the preparation method of a kind of electrode slurry.
Background technology
In lithium ion battery manufacture process, slurry mixed processes is the most important one procedure.Li-ion electrode is starched
Material generally comprises both positive and negative polarity active material, conductive agent, bonding agent.In order to improve the character such as the dispersibility of electrode slurry, stability,
Slurry can also add the additives such as stabilizer, dispersant or surfactant.Additionally, for other property improving battery
Can, slurry can also add other functional additives, such as nano aluminium oxide.In positive and negative electrode slurry, granulated activated
Dispersibility and the uniformity of material, conductive agent and functional additive will have influence on the lithium ion motion at battery two interpolar,
Therefore in lithium ion battery produces, the mixing dispersion of the slurry of each pole piece material is most important.The quality of slurry dust dispersion quality,
The capacity performance of battery, the most forthright, cyclicity and concordance there are is large effect, follow-up lithium ion battery can be directly influenced
The performance of the quality produced and products thereof.
During preparing electrode slurry, the mode of stirring is generally used to make the various components in slurry be sufficiently mixed all
Even, and there is certain viscosity, show preferable mobility simultaneously.Wherein crucial problem is to make the mixing of various component all
Even, next to that consider viscosity, mobility and solid content.
The alr mode of electrode slurry mainly has dry stirring and wet method stirring at present.As it is shown in figure 1, dry stirring is main
It is by after preliminary for each powder mix homogeneously, adds solvent and dispersant, it is achieved scattered effect.Dry mixed mixing speed
Comparatively fast, about 4-8 hour, but the uniformity of stirring is poor.As in figure 2 it is shown, wet method stirring is first glue, it is subsequently adding conductive agent
Stirring, adds major ingredient (i.e. active substance) stirring.The used time of wet method stirring is longer, generally higher than 8 hours, the uniformity of stirring
Higher than dry stirring.
In electrode slurry, each component dispersion effect in different environments is different.Conductive agent is usually and uses nano-scale
White carbon black, such as Super P (SP type carbon black conductive agent), acetylene black, KS series carbon particulate, carbon fiber, CNT (CNT), section
Qin is black.It is generally believed that owing to the particle size of nano-particle is little, surface area is big, so the dispersibility of nano-particle can phase
To poor.
CN104466111A discloses the preparation technology of a kind of lithium electrode slurry, by rubber powder, conductive agent, active substance respectively
It is mixed and made into solution with solvent, then conductive agent solution, active substance solution and glue are mixed, finally add residual solvent mixing.
CN101694872A and CN103022433A discloses the manufacture method of a kind of li-ion electrode slurry mixing, is all
After conductive agent, active substance are dry mixed, then mix with binder solution.
How to make in li-ion electrode slurry that each component is scattered to be more uniformly distributed, thus improve lithium ion battery further
Electrical property, this is that those skilled in the art endeavour to solve the technical problem that always.
Summary of the invention
It is an object of the invention to the dispersion effect realizing such as improving electrode slurry, and/or shorten mixing time, and/
Or improve in the electrical property of battery or multinomial, concrete, such as, the normal capacity playing battery, and/or extend and follow
The ring life-span, and/or improve concordance.
Inventor, in order to realize above-mentioned one or entry, has carried out substantial amounts of experiment, it has unexpectedly been found that, use wet
Method stirs, in the environment of the least granule disperses, and the granule that preferential dispersion particle diameter is less, bigger with particle diameter the most again
Grain mixing, so can make particle diameter larger particles mix homogeneously with particle diameter smaller particle, reach more preferable dispersion effect.By this
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, and battery performance obtains
To improving.
In particular it relates to the preparation method of a kind of electrode slurry, described electrode slurry comprises particulate material,
Described particulate material includes the 1st particulate material, the 2nd particulate material ..., the (n-1)th particulate material, and the n-th granule
Shape material, wherein n is the natural number more than or equal to 3, and the order that the granularity of described particulate material is from small to large is: the 1st
Particulate material < the 2nd particulate material < ... < the (n-1)th particulate material < the n-th particulate material,
Described preparation method comprises the following steps:
1) in solvent, the 1st particulate material, mixing are added；
2) alternatively, to step 1) gained solution adds binder solution and/or thickener soln, mixing；
3) to step 2) in gained solution, to repeat step 1) and step 2) in the way of add the 2nd granular substance
Matter ..., the (n-1)th particulate material；
4) to step 3) gained solution adds the n-th particulate material, mixing；
5) alternatively, to step 4) gained solution adds thickening agent, mixing；
6) to step 5) gained solution adds binding agent, mixing, obtain electrode slurry.
In a preferred embodiment, the preparation method of electrode slurry of the present invention, wherein said granule
Shape material includes active substance, and (preferably lithium ion battery active substance, such as positive active material, including cobalt acid lithium, ternary
Material, LiMn2O4, or negative electrode active material, including Delanium, composite graphite, native graphite, Si-C composite material),
Alternatively, described particulate material also includes conductive agent, and (described conductive agent selected from Super P, (lead by SP type white carbon black
Electricity agent), acetylene black, KS series carbon particulate, carbon fiber, CNT (CNT), Ketjen black) or/and functional additive is (such as
Nano aluminium oxide).
In a preferred embodiment, the preparation method of the electrode slurry described in the aforementioned any one of the present invention, wherein
Described solvent is water or N-Methyl pyrrolidone.
In a preferred embodiment, the preparation method of the electrode slurry described in the aforementioned any one of the present invention, wherein
Described binder solution be polyvinylidene fluoride (including the homopolymer of vinylidene, copolymer or its modifier), polyacrylic acid,
The mixture of sodium alginate or butadiene-styrene rubber and described solvent.
In a preferred embodiment, the preparation method of the electrode slurry described in the aforementioned any one of the present invention, wherein
Described thickener soln is the mixture of hydroxymethyl cellulose and solvent.
In a preferred embodiment, the preparation method of the electrode slurry described in the aforementioned any one of the present invention, wherein
Step 2) binder solution that added and/or thickener soln be that all binding agents and/or thickening agent are molten needed for electrode slurry
The 0 of liquid～40% (preferably 1-40%, more preferably 10-30%, such as 20%),
Step 5) thickening agent that added is residue thickening agent,
Step 6) binding agent that added is residue binding agent.
In a preferred embodiment, the preparation method of the electrode slurry described in the aforementioned any one of the present invention, wherein
Described n is the natural number of 3～6, preferably 3,4,5 or 6.
In a preferred embodiment, the preparation method of the electrode slurry described in the aforementioned any one of the present invention, described
Electrode slurry is anode sizing agent, wherein: described particulate material includes that conductive agent and positive active material, described solvent are
N-Methyl pyrrolidone, described binder solution be polyvinylidene fluoride (include the homopolymer of vinylidene, copolymer or its
Modifier) and the mixture of described solvent.
In a preferred embodiment, the preparation method of the electrode slurry described in the aforementioned any one of the present invention, described
Electrode slurry is anode sizing agent, wherein: n be the 3, the 1st particulate material 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 electrode slurry described in the aforementioned any one of the present invention, described
Electrode slurry is anode sizing agent, and described preparation method comprises the following steps:
1) in described solvent, the 1st particulate material, mixing are added；
2) to step 1) gained solution adds the 2nd particulate material, mixing；
3) alternatively, to step 2) gained solution adds binder solution (all glue needed for being preferably added to electrode slurry
The 0 of mixture solution～40% (preferably 1-40%, more preferably 10-30%, such as 20%)), mixing；
4) to step 3) gained solution adds the 3rd particulate material, mixing；
5) to step 4) gained solution adds binding agent, mixing, to obtain final product.
In a preferred embodiment, the preparation method of the electrode slurry described in the aforementioned any one of the present invention, described
Electrode slurry is cathode size, wherein: described particulate material includes that conductive agent and negative electrode active material, described solvent are
Water, described thickener soln is hydroxymethyl cellulose and the mixture of described solvent, and described binder solution is butylbenzene rubber
Glue and the mixture of described solvent.
In a preferred embodiment, the preparation method of the electrode slurry described in the aforementioned any one of the present invention, described
Electrode slurry is cathode size, wherein: n be the 3, the 1st particulate material 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 electrode slurry described in the aforementioned any one of the present invention, described
Electrode slurry is cathode size, and described preparation method comprises the following steps:
1) in described solvent, the 1st particulate material, mixing are added；
2) to step 1) gained solution adds the 2nd particulate material, mixing；
3) alternatively, to step 2) gained solution adds thickener soln (all increase needed for being preferably added to electrode slurry
The 0 of thick agent solution～40% (preferably 1-40%, more preferably 10-30%, such as 20%)), mixing；
4) to step 3) gained solution adds the 3rd particulate material, mixing；
5) to step 4) gained solution adds thickening agent, mixing；
6) to step 5) gained solution adds binding agent, mixing, to obtain final product.
In a preferred embodiment, the preparation method of the electrode slurry described in the aforementioned any one of the present invention, wherein
The mode of mixing is stirring.
In a preferred embodiment, the preparation method of the electrode slurry described in the aforementioned any one of the present invention, wherein
Described binder solution and/or thickening agent are prepared by following preparation method: described binding agent and/or thickening agent are added
Mix in described solvent.Preferably, described binding agent and/or thickening agent join in described solvent in batches, each batch
Mix after addition, add next batch mixing, until whole binding agents and/or thickening agent add and mix, to obtain final product.
In a preferred embodiment, during preparing binder solution, described binding agent divides 1 batch to criticize to m and adds
Entering in solvent, m is 3,4 or 5, and the 1st batch of addition is about the half of the total addition of binding agent, and m-1 criticizes addition and is about surplus
The half of remaining binding agent, m criticizes addition residue binding agent.
In a preferred embodiment, during preparing binder solution, described binding agent joins in solvent
After, the method for mixing is: after adding every batch of binding agent, the most once stir, and uses 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 stirring again, use revolution 20-35r/min (such as 30r/min), rotation 1500-3000r/min (such as
2000r/min or 2500r/min) parameter vacuum stirring, mixing time is 40-150min (such as 60min or 120min).Stir
Mix number of times and the visual mixed effect of mixing time and be increased or decreased.Preferably, stirring is 20-60 DEG C (such as 45 DEG C) in temperature
Under carry out.
In a preferred embodiment, during preparing thickener soln, described thickening agent divides 1 batch to criticize to m and adds
Entering in solvent, m is 3,4 or 5, and the 1st batch of addition is about the half of the total addition of thickening agent, and m-1 criticizes addition and is about surplus
The half of remaining thickening agent, m criticizes addition residue thickening agent.
In a preferred embodiment, during preparing thickener soln, described thickening agent joins described molten
After in agent, the method for mixing is: after adding every batch of thickener soln, the most once stir, and uses 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 stirring again, use revolution 15-20r/min (such as 18r/min),
The parameter atmospheric agitation of rotation 700-1000r/min (such as 800r/min), mixing time is 15-30min (such as 20min)；
Carry out triple mixing the most again, use revolution 20-35r/min (such as 25r/min), rotation 1300-2500r/min (such as
1500r/min or 2000r/min) parameter vacuum stirring, mixing time is 30-150min (such as 60min or 120min).Often
Pressure stirs number of times and the visual mixed effect of mixing time and is increased or decreased.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 electrode slurry described in the aforementioned any one of the present invention, the 1st
Particulate matter add after, its mixed method is: the most once stir, use revolution 5-30r/min (such as 20r/min), from
Turning the parameter atmospheric agitation of 200-1500r/min (such as 400r/min, 800r/min or 1200r/min), mixing time is 5-
20min (such as 10min)；Carry out secondary stirring again, use revolution 15-35r/min (such as 25r/min or 30r/min), rotation
The parameter vacuum stirring of 1200-2000r/min (such as 1500r/min), mixing time be 20-60min (such as 30min or
40min)；Atmospheric agitation number of times and the visual mixed effect of mixing time and be increased or decreased；Preferably, stirring temperature be 20～
Carry out under 30 DEG C (such as 25 DEG C).
In a preferred embodiment, the preparation method of the electrode slurry described in the aforementioned any one of the present invention, the 2nd
Particulate matter add after, its mixed method is: the most once stir, use revolution 5-30r/min (such as 20r/min), from
Turning the parameter atmospheric agitation of 200-1500r/min (such as 400r/min, 800r/min or 1200r/min), mixing time is 5-
20min (such as 10min)；Carry out secondary stirring again, use revolution 15-35r/min (such as 25r/min or 30r/min), rotation
The parameter vacuum stirring of 1200-2000r/min (such as 1500r/min), mixing time be 20-60min (such as 30min or
40min)；Atmospheric agitation number of times and the visual mixed effect of mixing time and be increased or decreased；Preferably, stirring temperature be 20～
Carry out under 30 DEG C (such as 25 DEG C).
In a preferred embodiment, the preparation method of the electrode slurry described in the aforementioned any one of the present invention, the 3rd
Particulate matter divides 1 batch to criticize to m to join in solution, and the 1st batch of addition is about the half of the 3rd total addition of particulate material, and
M-1 criticizes addition and is about the half remaining the 3rd particulate material, and m criticizes addition residue the 3rd particulate material.Wherein m is 3,4
Or 5.
In a preferred embodiment, the preparation method of the electrode slurry described in the aforementioned any one of the present invention, each
After criticizing the 3rd particulate material addition, its mixed method is: the most once stir, and uses 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), during stirring
Between be 5-20min (such as 10min)；Carry out secondary stirring again, use 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)；Carry out triple mixing the most again, use revolution 15-35r/min (such as 20r/min or 30r/min), from
Turn the parameter vacuum stirring of 1300-2500r/min (such as 1500r/min), mixing time be 90-150min (such as
120min).Atmospheric agitation number of times and the visual mixed effect of mixing time and be increased or decreased.Preferably, stirring is 20 in temperature
～carry out under 30 DEG C (such as 25 DEG C).
In a preferred embodiment, the preparation method of the electrode slurry described in the aforementioned any one of the present invention, described
After binder solution adds, its mixed method is: the most once stir, employing revolution 5-20r/min (such as 15r/min),
The parameter atmospheric agitation of rotation 600-1200r/min (such as 800r/min), mixing time is 5-20min (such as 10min)；Again
Carry out secondary stirring, use revolution 20-35r/min (such as 30r/min), rotation 800-2000r/min (such as 1000r/min
Or 1500r/min) parameter atmospheric agitation, mixing time is 15-30min (such as 20min)；Carry out triple mixing the most again,
Revolution 15-35r/min (such as 30r/min), the parameter vacuum of rotation 2000-3000r/min (such as 2500r/min) is used to stir
Mixing, mixing time is 90-150min (such as 120min).Atmospheric agitation number of times and the visual mixed effect of mixing time and increase or
Reduce.Preferably, stirring is carried out under temperature is 20～30 DEG C (such as 25 DEG C).
In a preferred embodiment, the preparation method of the electrode slurry described in the aforementioned any one of the present invention, described
After thickener soln adds, its mixed method is: the most once stir, employing revolution 5-25r/min (such as 20r/min),
The parameter atmospheric agitation of rotation 600-1200r/min (such as 800r/min), mixing time is 5-20min (such as 10min)；Again
Carry out secondary stirring, use revolution 20-35r/min (such as 30r/min), rotation 2000-3500r/min (such as 2500r/
Min) parameter vacuum stirring, mixing time is 20-150min (such as 30min or 120min).Atmospheric agitation number of times and stirring
Time visual mixed effect and be increased or decreased.Preferably, stirring is carried out under temperature is 20～30 DEG C (such as 25 DEG C).
In a preferred embodiment, the preparation method of the electrode slurry described in the aforementioned any one of the present invention, wherein
Described vacuum refers to the environment of vacuum≤-0.08MPa.
The invention still further relates to a kind of electrode slurry, by the preparation method system of the electrode slurry described in the aforementioned any one of the present invention
For obtaining.
The invention still further relates to a kind of electrode plates, its surface-coated has electrode slurry of the present invention.
The invention still further relates to a kind of battery, wherein comprise electrode plates of the present invention.
Heretofore described battery, preferably secondary cell, more preferably lithium ion battery.
In the present invention, described electrode slurry includes cathode size and anode sizing agent.
In the present invention, binding agent used in anode sizing agent is not limited to PVDF, any material that can be used as positive electrode binder
Material is all applicable to the preparation method of the present invention.
In the present invention, thickening agent agent used in cathode size is not limited to CMC, and any material that can be used as thickening agent is equal
It is applicable to the preparation method of the present invention.
In the present invention, described " granularity " represents the mean size of particulate material.In one embodiment, institute of the present invention
" granularity " use " D50 " stated characterizes, and D50 is also meso-position radius or median particle diameter, and its implication is the cumulative particle sizes distribution of a sample
Percent reaches particle diameter corresponding when 50%.Its physical significance is that particle diameter is more than its granule and accounts for 50%, less than it
Grain also accounts for 50%.
Beneficial effects of the present invention:
The present invention, by optimizing charging sequence, optimizes slurry agitation technique, it is possible to obtain one or more has below
Benefit effect:
1, slurry respectively forms component scattered uniformity acquisition significantly improvement；
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 plays fully, concordance is high, have extended cycle life.
Accompanying drawing explanation
Dry powder stirring schematic flow sheet in Fig. 1 prior art；
Fig. 2 wet method of the prior art stirring schematic flow sheet；
The wet method stirring schematic flow sheet of Fig. 3 present invention；
The anode pole piece scanning electron microscope (SEM) photograph of the anode sizing agent coating that Fig. 4 is obtained by embodiment 1；
The anode pole piece scanning electron microscope (SEM) photograph of the anode sizing agent coating that Fig. 5 is obtained by comparative example 1；
The cathode pole piece scanning electron microscope (SEM) photograph of the anode sizing agent coating that Fig. 6 is obtained by embodiment 1；
The cathode pole piece scanning electron microscope (SEM) photograph of the anode sizing agent coating that Fig. 7 is obtained by comparative example 1；
The cyclic curve of the soft-package battery that the electrode slurry that Fig. 8 is obtained by embodiment 1 and comparative example 1 assembles.
Detailed description of the invention
Below in conjunction with embodiment, embodiment of the present invention are described in detail, but those skilled in the art will
Understanding, the following example is merely to illustrate the present invention, and should not be taken as limiting the scope of the invention.In embodiment unreceipted specifically
Condition person, the condition advised according to normal condition or manufacturer is carried out.Agents useful for same or instrument unreceipted production firm person, be
Can by city available from conventional products.
In example below, finely ground particle substance of the present invention is conductive agent, such as SP type carbon black conductive agent, SK-6 type stone
Ink conductive agent；Described large particulate matter is active substance, such as Delanium, cobalt acid lithium.
As it is shown on figure 3, in an embodiment of the invention, the preparation method of the present invention is: prepare simultaneously glue and
Conductive agent solution, after prepared by conductive agent solution, is the most first dividedly in some parts active substance, after mix homogeneously, more in batches
Add glue, mix homogeneously, again binding agent being added mix homogeneously if had, obtaining positive and negative electrode glue.
In example below or experimental example, without specified otherwise, percentage sign " % " is all percentage by weight.
Without specified otherwise, " vacuum " described in example below refers to the environment of vacuum≤-0.08MPa.
In example below or experimental example, the equipment used by stirring is that (30L, the red cloud in Guangzhou mixes vacuum mixer
Equipment company limited)
In the present invention, " viscosity " can use universal test canonical measure in industry.Such as, example below or experimental example
In, use the viscosimeter (U.S. Brookfield) that model is LVDV-C to measure the viscosity of the electrode slurry obtained.
In example below, solid content is the percentage by weight 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 10%, and PVDF joins in solvent NMP at twice, stirring technique and effect
As shown in table 2, whipping temp is 45 DEG C, about 4 hours used times, obtains positive electrode binder solution.
Table 2
2) conductive agent solution is prepared
The preparation of conductive agent solution is carried out with the preparation of positive electrode binder solution the most simultaneously.By conductive agent and solvent NMP
Stir after mixing.First weigh solvent NMP, join in agitated kettle, then conductive agent is added at twice, add SP for the first time
Type carbon black conductive agent, second time adds KS-6 type graphite agent, and stirring technique and effect are shown in Table 3, and whipping temp is 25 DEG C, uses
Time about 1.5 hours, obtain conductive agent solution.
Table 3
3) in conduction agent solution, active substance and binder solution are added
Active substance LCO is joined in three times in conductive agent solution, after stirring, add binder solution, enter
The stirring that row is last.Concrete stirring technique is shown in Table 4, and whipping temp is 25 DEG C.Wherein, after active substance all adds, total
Mixing time is about 2.5 hours.Now, positive electrode binder solution has just stirred.It is subsequently adding glue, is stirred for about 3 little
Time, slurry agitation completes.Slurry agitation total used time is about 7 hours.
Table 4
After having stirred, obtaining the anode sizing agent that solid content is 70%, slurry fluidity is good, agglomerating existing without obvious granule
As, recording viscosity is 5400Cp.
2. the preparation of cathode size
The formula of cathode size is as shown in table 5.
Table 5
1) negative pole thickener soln is prepared
The concentration of negative pole thickener soln is 3%, and CMC adds at twice, and stirring technique is as shown in table 6, and whipping temp is
45 DEG C, about 3.5 hours used times, obtain negative pole thickener soln.
Table 6
2) conductive agent solution is prepared
The preparation of conductive agent solution is carried out with the preparation of negative pole thickener soln the most simultaneously, adds conduction the most at twice
Agent, solvent is water, adds SP type carbon black conductive agent for the first time, and second time adds KS-6 type graphite agent, stirring technique and effect
Fruit is shown in Table 7, and whipping temp is about 1 hour 25 DEG C of used time, obtains conductive agent solution.
Table 7
3) in conduction agent solution, active substance and negative pole thickener soln are added
After conductive agent solution stirring completes, in three times active substance is added in conductive agent solution, after stirring, finally
Adding negative pole thickener soln, mix, stirring technique is as shown in table 8, and whipping temp is 25 DEG C.Delanium has stirred
About 2.5 hours used times, adding the mixing time (about 1 hour) of conductive agent solution, time shared about 3.5 hours, now, glue was just
Stirring completes.Then weigh the amount of required glue, join at twice in the solution containing conductive agent and active substance, stir
Mix, about 3 hours used times.Finally add the SBR aqueous solution that concentration is 45%, continue stirring, about 1.5 hours used times.
Table 8
After having stirred, about 8 hours total used times, obtaining the cathode size that solid content is 43%, slurry fluidity is good, records
Viscosity is 4000Cp.
Binding agent used in pole slurry in this enforcement is not limited to PVDF, any material that can be used as positive electrode binder
All it is applicable to the preparation method of the present invention.Thickening agent agent used in cathode size is not limited to CMC, any can be used as thickening agent
Material be all applicable to the preparation method of the present invention.
Embodiment 2
In the preparation method of heretofore described electrode slurry, it is also possible to after prepared by conductive agent solution, first add
Enter binder solution or the thickener soln of 10-60%, after stirring, then add active substance and remaining bonding in batches
Agent solution or thickener soln.
The preparation of the anode sizing agent in the present embodiment, first adds the binder solution of 30%, specifically in conductive agent solution
Stirring technique is shown in Table 9, and whipping temp is 25 DEG C, and after stirring, then batch adds active substance and remaining binder solution.
The preparation method of binder solution is same with embodiment 1, active substance and the Adding Way of residue binder solution and stirring technique
Embodiment 1.
Table 9
In embodiment 2, in electrode slurry preparation process, in conductive agent solution, first add some adhesive solution, make
Conductive agent solution has certain viscosity, therefore can carry out the higher dispersion stirring speed, can obtain uniform dispersion effect equally.
Comparative example 1
As in figure 2 it is shown, use traditional wet method stirring means to carry out slurry agitation, the same embodiment of formula of anode and cathode slurry
1。
The stirring technique of anode sizing agent is shown in Table 10, and about 11.5 hours total used times, whipping temp whole process is 25 DEG C.Stirring completes
After, obtaining anode sizing agent, slurry viscosity is 6300Cp.
Table 10
The stirring technique of cathode size is shown in Table 11, and about 10 hours used times, whipping temp whole process is 25 DEG C.After having stirred,
Obtaining cathode size, slurry viscosity is 4000Cp.
Table 11
The dispersion effect of the different preparation method of experimental example 1
After being completed by the positive and negative electrode slurry agitation that embodiment 1 and comparative example 1 obtain, carry out sieving, being coated with, it is thus achieved that positive and negative
Pole pole piece.Positive and negative plate is scanned electron microscopic observation, investigates the effect of slurry agitation.Electronic Speculum model is FEI
Quanta650F。
Be can be observed by Fig. 4 to Fig. 7, the slurry that the preparation method of the employing present invention and traditional preparation methods are obtained, point
After not being coated, its uniformity has marked difference, and concrete comparing result is shown in Table 12.
Table 12
Experimental example 2 electrical property experiment
In order to verify the advantage of preparation method that the present invention provides further, respectively embodiment 1 and comparative example 1 are obtained
Positive and negative electrode slurry is coated respectively and prepares pole piece, the pole piece of acquisition is carried out roll-in, point bar, 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, concrete technological parameter and equipment
Model is shown in Table 13.Vacuum drying, fluid injection, fixture baking all use this area conventional method to carry out.
Technological parameter and the equipment of soft-package battery prepared by table 13
Made soft-package battery is carried out volume test and cycle performance test.
The method of volume test is: 2000mA constant-current constant-voltage charging to 4.35V, cut-off current 200mA；After standing 10min,
2000mA constant-current discharge, to 3.0V, stands 10min.Above 3 times of circulation, takes the capacity that last discharge capacity is battery.
The result of volume test is as shown in table 14, uses the battery of the assembled acquisition of electrode slurry of comparative example 1 acquisition, holds
Amount average out to 4170mAh, gram specific capacity average out to 155.5mAh/g of cobalt acid lithium.Use the electrode that the embodiment of the present invention 1 obtains
The battery of the assembled acquisition of slurry, capacity average out to 4236.3mAh, corresponding gram specific capacity is 158.2mAh/g.Visible, this
The electrode slurry that the preparation method of bright offer obtains can make the volumetric properties of battery get a promotion.
Table 14 volume test result
The method of testing of cycle performance is: 2000mA constant-current constant-voltage charging to 4.35V, cut-off current 200mA；Stand
After 10min, 2000mA constant-current discharge to 3.0V, stand 10min.Persistently carry out above circulation.Loop test result is shown in Fig. 8, adopts
The circulating battery that the electrode slurry obtained by comparative example 1 assembles 155 times, the electrode slurry using embodiment 1 to obtain assembles
Circulating battery 160 times.
As seen from Figure 8, the cycle performance of the battery that the electrode slurry using embodiment 1 to obtain is assembled into is apparently higher than employing
The cycle performance of the battery that the electrode slurry that comparative example 1 obtains is assembled into.They hold in the circulation of 50 times, 100 times and 150 times
Amount conservation rate correction data is shown in Table 15.
The partial results of table 15 cycle performance test
Although the detailed description of the invention of the present invention has obtained detailed description, it will be understood to those of skill in the art that root
According to disclosed all teachings, those details can be carried out various amendment and replacement, these change all the guarantor of the present invention
Within the scope of protecting.The four corner of the present invention is given by claims and any equivalent thereof.
Claims (18)
1. a preparation method for electrode slurry, comprises particulate material in described electrode slurry, described particulate material includes
1st particulate material, the 2nd particulate material ..., the (n-1)th particulate material, and the n-th particulate material, wherein n is for being more than
Or the natural number equal to 3, and the order that the granularity of described particulate material is from small to large is: the 1st particulate material < the 2nd granule
Shape material < ... < the (n-1)th particulate material < the n-th particulate material,
Described preparation method comprises the following steps:
1) in solvent, the 1st particulate material, mixing are added；
2) alternatively, to step 1) gained solution adds binder solution and/or thickener soln, mixing；
3) to step 2) in gained solution, to repeat step 1) and step 2) in the way of add the 2nd particulate material ...,
N-1 particulate material；
4) to step 3) gained solution adds the n-th particulate material, mixing；
5) alternatively, to step 4) gained solution adds thickening agent, mixing；
6) to step 5) gained solution adds binding agent, mixing, obtain electrode slurry.
2. the preparation method described in claim 1, described particulate material includes active substance (preferably lithium ion battery activity
Material, such as positive active material, including cobalt acid lithium, ternary material, LiMn2O4, or negative electrode active material, including Delanium,
Composite graphite, native graphite, Si-C composite material),
Alternatively, described particulate material also include conductive agent (described conductive agent selected from Super P (SP type carbon black conductive agent),
Acetylene black, KS series carbon particulate, carbon fiber, CNT (CNT), Ketjen black) or/and functional additive (such as nano oxygen
Change aluminum).
3. the preparation method described in any one of claim 1 to 2, wherein said solvent is water or N-Methyl pyrrolidone.
4. the preparation method described in any one of claims 1 to 3, wherein said binder solution is that polyvinylidene fluoride (includes
The homopolymer of vinylidene, copolymer or its modifier), polyacrylic acid, sodium alginate or butadiene-styrene rubber mixed with described solvent
Compound.
5. the preparation method described in any one of Claims 1-4, wherein said thickener soln is hydroxymethyl cellulose and solvent
Mixture.
6. the preparation method described in any one of claim 1 to 5, wherein step 2) binder solution that added and/or thickening
Agent solution be needed for electrode slurry all binding agents and/or the 0 of thickener soln～40% (preferably 1-40%, the most excellent
Elect 10-30% as, such as 20%),
Step 5) thickening agent that added is residue thickening agent,
Step 6) binding agent that added is residue binding agent.
7. the preparation method described in any one of claim 1 to 6, wherein said n is the natural number of 3～6, preferably 3,4,5 or
6。
8. the preparation method described in any one of claim 1-7, wherein: described electrode slurry is anode sizing agent, described graininess
Material includes that conductive agent and positive active material, described solvent are N-Methyl pyrrolidone, and described binder solution is poly-inclined two
Fluorothene (including the homopolymer of vinylidene, copolymer or its modifier) and the mixture of described solvent.
9. the preparation method described in claim 8, wherein: n be the 3, the 1st particulate material be that carbon black conductive agent is (such as SP type white 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.
10. the preparation method described in claim 9, comprises the following steps:
1) in described solvent, the 1st particulate material, mixing are added；
2) to step 1) gained solution adds the 2nd particulate material, mixing；
3) alternatively, to step 2) gained solution adds binder solution, mixing；
4) to step 3) gained solution adds the 3rd particulate material, mixing；
5) to step 4) gained solution adds binding agent, mixing, to obtain final product.
Preparation method described in 11. any one of claim 1-7, wherein: described electrode slurry is cathode size, described graininess
Material includes that conductive agent and negative electrode active material, described solvent are water, and described thickener soln is hydroxymethyl cellulose and described
The mixture of solvent, described binder solution is butadiene-styrene rubber and the mixture of described solvent.
Preparation method described in 12. claim 11, wherein: n be the 3, the 1st particulate material be that carbon black conductive agent is (such as SP type charcoal
Black conductive agent), the 2nd particulate material is graphite agent (such as KS-6 type graphite agent), and the 3rd particulate material is that negative pole is lived
Property material.
Preparation method described in 13. claim 12, comprises the following steps:
1) in described solvent, the 1st particulate material, mixing are added；
2) to step 1) gained solution adds the 2nd particulate material, mixing；
3) alternatively, to step 2) gained solution adds thickener soln, mixing；
4) to step 3) gained solution adds the 3rd particulate material, mixing；
5) to step 4) gained solution adds thickening agent, mixing；
6) to step 5) gained solution adds binding agent, mixing, to obtain final product.
Preparation method described in 14. any one of claim 1 to 12, the mode wherein mixed is stirring.
Preparation method described in 15. any one of claim 1 to 14, wherein said binder solution and/or thickening agent are by following
Preparation method prepares: described binding agent and/or thickening agent is joined in described solvent and mixes；
Preferably, described binding agent and/or thickening agent join in described solvent in batches, and each batch mixes after adding, then
Add next batch mixing, until whole binding agents and/or thickening agent add and mix, to obtain final product.
16. 1 kinds of electrode slurrys, are prepared by the preparation method described in any one of claim 1 to 15.
17. 1 kinds of electrode plates, its surface-coated is had the right the electrode slurry described in requirement 16.
18. 1 kinds of batteries, wherein comprise the electrode plates described in claim 17.
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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 |
| CN109378468A (en) * | 2018-11-28 | 2019-02-22 | 邓丽萍 | A kind of pulping process of the ternary material for lithium ion battery |
| CN109758960A (en) * | 2019-03-07 | 2019-05-17 | 广东宏工物料自动化***有限公司 | Lithium ion battery positive and negative electrode slurry mixture manufacturing system and blank preparation technics |
| CN111081970A (en) * | 2019-12-25 | 2020-04-28 | 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 |
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| CN109758960A (en) * | 2019-03-07 | 2019-05-17 | 广东宏工物料自动化***有限公司 | Lithium ion battery positive and negative electrode slurry mixture manufacturing system and blank preparation technics |
| CN111081970A (en) * | 2019-12-25 | 2020-04-28 | 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 |
| CN114628662A (en) * | 2021-10-08 | 2022-06-14 | 万向一二三股份公司 | Preparation method for improving solid content of lithium battery anode slurry |
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