CN104854737B - The manufacture method of lithium ion secondary battery negative pole slurries - Google Patents

The manufacture method of lithium ion secondary battery negative pole slurries Download PDF

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Publication number
CN104854737B
CN104854737B CN201380063111.0A CN201380063111A CN104854737B CN 104854737 B CN104854737 B CN 104854737B CN 201380063111 A CN201380063111 A CN 201380063111A CN 104854737 B CN104854737 B CN 104854737B
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China
Prior art keywords
secondary battery
lithium ion
slurries
ion secondary
negative pole
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CN104854737A (en
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香野大辅
田中麻纱子
海川敏光
武内正隆
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Resonac Holdings Corp
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Showa Denko KK
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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
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • 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
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

A kind of manufacture method of lithium ion secondary battery negative pole slurries, with agitating procedure, the process is stirred to the mixture containing tackifier solution and dispersate, the dispersate includes negative electrode active material, and the agitating procedure includes weighted average (α) (m to the specific surface area of the dispersate2/ g) process that is stirred with mixture that the product (α × β) of solid constituent ratio (β) is more than 1.3, and the process that does not include individually adding the decentralized medium for slurries or below 5 mass % that the amount of the decentralized medium individually added in the case of including the process is the decentralized medium total amount in slurries.

Description

The manufacture method of lithium ion secondary battery negative pole slurries
Technical field
The present invention relates to the method for manufacture lithium secondary battery anode slurries.Moreover, it relates to obtained using the preparation method To slurries, pass through lithium ion secondary of the lithium ion secondary battery negative pole that the slurries manufacture with pole plate and comprising the pole plate Battery.
Background technology
The small portable devices such as mobile phone, video camera are not only, the electricity as electric bicycle, various electric automobiles etc. Source, lithium rechargeable battery are widely used due to feature as high-energy-density, high voltage.As the secondary electricity of these lithiums Negative material used in pond, it may be used at the stone big with the charge/discharge capacity of per unit mass under the close low potential of lithium (Li) Carbon material representated by ink.In addition, as negative pole adhesive, mainly (it is referred to as using polyvinylidene fluoride up to now PVdF the fluororesin) and its representated by copolymer, but in the case of using these adhesives, needed to use as solvent organic Solvent.Recently, slurries manufacturing process simplification etc. is made because butadiene-styrene rubber (referred to as SBR) can utilize as aqueous dispersions Advantage, therefore usually use.
As the manufacture method of slurries, such as Japanese Unexamined Patent Publication 2009-187819 publications (patent document 1) are like that, propose Manage by the viscosity of slurries the manufacture method of the termination condition of process.In addition, low resistance, long lifetime from battery From the viewpoint of, gas-phase growth of carbon fibre is added sometimes.In this case, such as Japanese Unexamined Patent Publication 2005-222933 publications (WO2005/067081) (patent document 2) is such, it is proposed that is added after carbon fiber is added into tackifier water solution and is stirred Negative material, SBR aqueous dispersions and the manufacture method stirred are added after further stirring, and it is negative being added to tackifier water solution The manufacture method of SBR aqueous dispersions and stirring is added after pole material and stirring after addition carbon fiber, further stirring.
Citation
Patent document 1：Japanese Unexamined Patent Publication 2009-187819 publications
Patent document 2：Japanese Unexamined Patent Publication 2005-222933 publications (WO2005/067081)
The content of the invention
In patent document 1, the manufacturing process of slurries is managed due to the current value by viscosity, device, therefore exist Following problems：Even if there is the cohesion block of scattered uneven part and/or electrode active material etc. in slurries, if addition is scattered Agent makes the reduction of solid constituent ratio, then the viscosity of slurries, current value reduce, hence into subsequent processing.Also, exist if Adjustment viscosity and in manufacturing process a large amount of addition dispersant monomers, then resulting slurries are being coated on collector and made When it is dried, problem as the adaptation reduction at the interface of collector and mixture layer.
The manufacture method of lithium ion secondary battery negative pole slurries in the preferred embodiment of the present invention, using passing through this The negative pole pole plate and battery of the slurries of method manufacture are as described below.
[1] a kind of manufacture method of lithium ion secondary battery negative pole slurries, has agitating procedure, the process is to containing increasing Stick solution and the mixture of dispersate are stirred, and the dispersate includes negative electrode active material, and the agitating procedure includes To weighted average (α) (m of the specific surface area of the dispersate2/ g) with the product (α × β) of solid constituent ratio (β) for 1.3 with On the process that is stirred of mixture, and do not include individually adding the process of the decentralized medium for slurries or wrapping The amount of the decentralized medium individually added in the case of including the process is below the 5 mass % of the decentralized medium total amount in slurries.
[2] manufacture method for the lithium ion secondary battery negative pole slurries that according to [1] is recorded, the agitating procedure bag Include the process adding tackifier solution to the dispersate and stir and by further addition tackifier solution and stir thereafter The process that operation carries out 1 time or is repeated more than 2 times.
[3] manufacture method for the lithium ion secondary battery negative pole slurries that according to [2] are recorded, the agitating procedure bag Include：
The process that the total amount of the dispersate is put into mixer；With
Next, the process that the operation for putting into tackifier solution to the mixer and stirring is repeated more than 2 times.
[4] manufacture method for the lithium ion secondary battery negative pole slurries that according to [3] are recorded, in initial Beater operator The amount of the tackifier solution put into sequence is 5~40 mass % of total usage amount of tackifier solution.
[5] according to described in [1] record lithium ion secondary battery negative pole slurries manufacture method, tackifier solution it is molten Agent includes water.
[6] manufacture method for the lithium ion secondary battery negative pole slurries that according to [1] is recorded, to containing tackifier After the process that solution and the mixture of dispersate are stirred, have and put into binder solution and the work stirred thereto Sequence.
[7] manufacture method for the lithium ion secondary battery negative pole slurries that according to [1] is recorded, the negative electrode active material Matter is more than a kind in non-graphite system carbon material and graphite system carbon material.
[8] manufacture method for the lithium ion secondary battery negative pole slurries that according to [1] is recorded, negative electrode active material The average grain diameter (D50) for the volume reference that laser diffractometry obtains is used as 1~50 μm.
[9] manufacture method for the lithium ion secondary battery negative pole slurries that according to [6] are recorded, described adhesive solution In contained adhesive ingredients be selected from butadiene-styrene rubber (SBR), nitrile rubber (NBR), butadiene rubber (BR), polystyrene- It is at least one kind of in acrylate (St-Ac), polyacrylonitrile (PAN) and polyamide-imides.
[10] manufacture method for the lithium ion secondary battery cathode slurries that according to [1] is recorded, the dispersate Include conductive auxiliary agent.
[11] a kind of lithium ion secondary battery negative pole slurries, manufactured using the either method of [1]~[10], Obtained using fineness-of-grind gauge according to the particle size that JIS K5600-2-5 are determined for negative electrode active material using laser diffractometry 90% accumulation particle diameter (D90) of the volume reference arrived is below.
[12] a kind of lithium ion secondary battery negative pole pole plate, it is the lithium rechargeable battery recorded by by described in [11] Negative pole is obtained from slurries are coated on collector and are dried.
[13] a kind of lithium rechargeable battery, the lithium ion secondary battery negative pole pole recorded comprising [11] or [12] Plate.
By using the lithium ion secondary battery negative pole pulp manufacturing processes of the present invention, active material decile can be manufactured Scattered matter is not condensed and shows the slurries of good dispersity, can be obtained when being coated with, being dried to collector, in slurries The lithium ion secondary battery cathode pole plate of part (mixture) that is dry and the being formed adaptation high with the interface display of collector.
Brief description of the drawings
Fig. 1 is one of the photo of the mixture part obtained in example 2 by SEM shootings.A and b is graphite particle One of enlarged drawing.
Fig. 2 is one of the photo of the mixture part obtained by SEM shootings in comparative example 2.C is the portion of carbon black cohesion The enlarged drawing divided, d and e are one of the enlarged drawing of graphite particle.
Fig. 3 is the slurries obtained in the embodiment 2 and comparative example 2 evaluated using fineness-of-grind gauge (grind gauge) Evaluate photo one.
Embodiment
The manufacture method of lithium ion secondary battery negative pole slurries in the preferred embodiment of the present invention includes Beater operator Sequence, the process are stirred to the mixture containing tackifier solution and dispersate.In addition, in the preferred embodiment of the present invention In, after the agitating procedure, including input binder solution and the process of stirring.
1. dispersate
Dispersate includes negative electrode active material, and conductive auxiliary agent etc. can be included as optional member.
1-1. negative electrode active material
It is as long as the material that negative electrode active material can use as the negative electrode active material of lithium rechargeable battery, specific Ground is that the material with the ability for electrochemically absorbing and releasing ion is just not particularly limited.
Improved from the wetability with scattered matchmaker, from the viewpoint of easy operation, pole strength, electrolyte retentivity, It is favourable that the specific surface area of negative electrode active material is as high as possible.Specifically, specific surface area is preferably 1m2/ more than g.It is another Aspect, if specific surface area is too high, side reaction easily occurs with electrolyte, therefore the upper limit of specific surface area is preferably 7m2/g。 The scope of preferred specific surface area is 1.0~7.0m2/ g, more preferably 1.5~6.0m2/g。
Specific surface area represents the ratio using BET method measure except except there is special note in this manual Surface area.
Negative electrode active material is preferably the material for including carbon.
As the material comprising carbon, non-graphite system carbon material, graphite system carbon material or their mixture can be enumerated, specifically For, there are Delanium, native graphite, amorphous graphite, soft carbon and hard carbon etc..
Non-graphite system carbon material is the carbon material of the three-dimensional crystal order without graphite, includes Turbostratic carbon materials Material, amorphous carbon material.In specific non-graphite system carbon material, make crystallization comprising vitreous carbon, because heat treatment temperature is low The carbon material not being in progress.As more specifically non-graphite system carbon material, can enumerate to the difficult graphite system macromolecule such as phenolic resin Carbon material that compound is heat-treated and formed, to pitch, coke in 1000 DEG C or so the carbon materials for being heat-treated and being formed Material, Electroconductivity of Conducting Polymers equiconjugate system high-molecular compound is heat-treated and formed carbon material, using hot CVD Method and be piled up in CVD carbon of substrate etc..In addition, Si can also be mixed into the respective heat treatment, thus can also increase Capacitance as negative pole.
The average grain diameter of non-graphite system carbon material without same, is not particularly limited according to the electrode plate shape as target, but In general, the average grain diameter (D50) of the volume reference that laser diffractometry obtains is used as 1~50 μm of scope.
Use the bulk density of the negative material in the case of non-graphite system carbon material, the real density of non-graphite system carbon material It is different, it is not particularly limited, but in general, the real density of non-graphite system carbon material is 1.9g/cm3More than, include negative pole The density (electrode volume density) of the mixture layer of active material, adhesive and conductive auxiliary agent is 1.5g/cm3More than, it is further excellent Elect 1.7g/cm as3More than.
Graphite system carbon material is the carbon material of the three-dimensional crystal order with graphite, can be used secondary generally as lithium The active carbon material material of battery and native graphite, the Delanium used.Delanium can be for example, by easy graphite The property changed carbon material is heat-treated and obtained.In addition, also include make from fusant graphite separate out again obtained from kish.
The crystallinity of graphite system carbon material is flourishing, and the insertion of Li ions, which departs from, equably to be occurred, and diffusion is also fast, therefore has The change of the discharge potential of battery is small, and high load characteristics also excellent such feature.The real density of graphite system carbon material is high Up to 2.2g/cm3Left and right, bulk density (electrode volume density) that can be in the case of as electrode is 1.5g/cm3It is used above. And porosity can also be reduced, electrode volume density is turned into 1.7g/cm3More than.
The graphite system carbon material, can be used the average grain diameter (D50) of volume reference obtained by laser diffractometry be 1~ 50 μm or so of material.The preferred crystallinity of the graphite system carbon material is high, the C in 002 face preferably in X-ray diffraction measure0For 0.6900nm(d002=0.3450nm) below, La (crystallite dimension of a direction of principal axis) is more than 100nm, Lc (the crystallite chis in c-axis direction It is very little) also greater than 100nm.In addition, Laser Raman R value is preferably 0.01~0.9 (R values：Obtained by laser Raman spectroscopy 1360cm-1Peak intensity relative to 1580cm-1Peak intensity ratio).
If to the graphite system carbon material addition boron and be heat-treated, crystallinity improves, and then suitable with electrolyte Ying Xing, stability are improved, therefore preferably.The addition of boron is not particularly limited, but if addition is crossed does not have effect at least, At most remained if crossed as impurity, thus it is not preferred.Preferable addition is in terms of boron atom conversion, in graphite system carbon material For the mass ppm of the mass ppm of 0.1 mass ppm~100000, more preferably 10 mass ppm~50000 scope.
1-2. optional member
As including carbon fiber, carbon black or its mixture in the conductive auxiliary agent of optional member.
As carbon black, furnace black, acetylene black and Ketjen black etc. can be used, preferably its average primary particle diameter be 10~100nm, Specific surface area is 10~100m2/g。
As carbon fiber, CNT and carbon fiber etc. can be used, preferably its average fiber footpath is 5~500nm, averagely Fiber is a length of 0.5~100 μm, specific surface area is 1~300m2/g。
Good conductive path can be formed between negative electrode active material particle by adding conductive auxiliary agent, contributes to battery Low resistance and long lifetime.In the case of adding conductive auxiliary agent, its use level is preferably 0.01~10 matter in dispersate Measure %, more preferably 0.1~5 mass %.If conductive auxiliary agent is excessive, the amount of negative electrode active material is relatively reduced, Battery capacity is caused to reduce.
2. tackifier solution
Tackifier solution is used for the viscosity for adjusting slurries.
As tackifier, such as polyethylene glycols, cellulose family, polyacrylamide, poly N-vinyl acid amides can be enumerated Class, poly N-vinyl pyrrolidone class etc..Among them, the preferred cellulose such as polyethylene glycols, carboxymethyl cellulose (CMC) Class, particularly preferred CMC.The use level of tackifier, in the case where the dispersate is set into 100 mass parts, preferably 0.1~ 10 mass parts, more preferably 0.3~3 mass parts.
The solvent of tackifier solution can enumerate water, alcohol (methanol, ethanol, propyl alcohol, butanol, isopropanol etc.) etc., and they can be with It is used alone or as a mixture.Preferable solvent is water.
The concentration of tackifier in tackifier solution is that viscosity can be made to turn into 50~5000mPas, preferably at room temperature For 100~3000mPas concentration, it is often preferred that 0.5~5 mass % scope.
3. agitating procedure
Mixture containing the tackifier solution and the dispersate is stirred.
The mixture is in stirring, weighted average (α) (m of the specific surface area of dispersate2/ g) and solid constituent ratio The product (α × β) of rate (β) is preferably more than 1.3.More preferably described product is more than 2.0, and the further preferred product is more than 2.4. The upper limit of the product is not particularly limited, but preferably less than 7.0, more preferably less than 6.0.
The viscosity of slurries is preferably regulated as the appropriate scope in view of slurries painting process.The viscosity of slurries is in solid constituent Ratio fix in the case of, if dispersate specific surface area greatly if increase.Generally, in the case of slurry viscosity identical, point Dissipate matter specific surface area it is big when solid constituent ratio step-down, on the contrary specific surface area hour solid constituent ratio uprise.
By weighted average (the α) (m for contrasting surface area2/ g) with the product (α × β) of solid constituent ratio (β) above-mentioned In the range of mixture be stirred, the generation of the cohesion grain of dispersate is inhibited, and dispersate is disperseed well.In addition, i.e. Make in the case of using conductive auxiliary agent, by being stirred to the mixture in the scope of above-mentioned product, conductive auxiliary agent Dispersiveness also greatly improves.
In this manual, " weighted average (α) (m of the specific surface area of dispersate2/ g) " in the single feelings of dispersate Its specific surface area (m is represented under condition2/ g), mean the ratio of each dispersate in the case where dispersate is the mixture of multiple compositions Weighted average (the m of surface area2/g).For example, it is x (m that dispersate, which is specific surface area,2/ g) active material a (g) with than surface Product is y (m2/ g) conductive auxiliary agent b (g) mixture in the case of, average weighted specific surface area is calculated as (xa+yb)/(a+ b)(m2/g)。
In addition, the composition of the quality of decentralized medium is subtracted among the gross mass that " solid constituent ratio (β) " means to put into Ratio, be by slurries it is coated and dried after residual solid constituent ratio.In solid constituent, except the dispersate with Outside, also comprising tackifier, adhesive ingredients described later.The value of the ratio is 0~1 scope.Furthermore in the dispersate, no Include tackifier and adhesive described later.
In the case of manufacturing slurries, carry out only adding decentralized medium in terminal stage to be adjusted to it is expected extensively all the time Viscosity the practice.But in the case of only adding decentralized medium for viscosity adjustment and stirring, easily cause tackifier molten Liquid, binder solution and the uneven mixing of the decentralized medium of addition are so that slurries are uneven.If the decentralized medium of addition Amount increases, then the tendency becomes obvious.If slurries become uneven, the collector of electrode and the interface of slurries (mixture) Adaptation reduces.Therefore, the process for individually adding the decentralized medium for slurries is not preferably included in the present invention.In addition in list Solely addition decentralized medium in the case of, its addition be preferably manufacture slurries in total score dispersion media amount 5 mass % with Under, more preferably below 1 mass %.In the present invention have need not by terminal stage only add decentralized medium come The advantages of adjusting viscosity.
The decentralized medium mentioned in this manual is the liquid parts for manufacturing slurries, without tackifier, adhesive, By the way that slurries are coated and dried, its major part is removed.
In the preferred embodiment of the present invention, the agitating procedure includes adding tackifier solution to the dispersate and stirred The process mixed and the work for operating progress 1 time or being repeated more than 2 times that will further add tackifier solution thereafter and stir Sequence.That is, the addition of tackifier and stirring are repeated more than 2 groups.
In the preferred embodiment of the present invention, preferably initially by the total amount input mixer of dispersate.That is, in the present invention Further preferred embodiment in, the agitating procedure includes：
The process that the total amount of dispersate is put into mixer；With next,
The process that the operation for putting into tackifier solution to the mixer and stirring is repeated more than 2 times.The situation Under, due to the stirring of the 2nd time when the stirring of the 1st time compared with, enter in the state of more than the total amount of the tackifier solution of input OK, the product of mixture when therefore the 2nd time is stirred is smaller than the 1st time.
By carrying out input and the stirring of multiple tackifier solution, it can further suppress the cohesion of the dispersate.
In the case of multiple tackifier solution input and stirring is made as above, thrown in initial agitating procedure 5~40 mass % of the total amount of the amount of the tackifier solution entered, preferably tackifier solution.More preferably 6~30 mass %.It is logical After the tackifier solution for initially putting into the scope, it can further suppress the cohesion of the dispersate.
The number of occurrence is more than 2 times, by carrying out further suppressing to condense for more than 3 times, therefore preferably.On Limit is not particularly limited, but if it is excessively at most economically disadvantageous, therefore preferably less than 5 times, more preferably less than 4 times.
In the case of carrying out multiple tackifier solution input and the process of stirring, at least 1 time therein is in the product In the range of the process that is stirred of mixture.For example, it is being stirred for the mixture of particular value to the product Afterwards, further liquid component or the dispersate such as addition tackifier solution, modulation are mixed with the product different from described value thereto In the case of being stirred for after compound, at least 1 process therein is that the mixture in the scope of the product is stirred Process.By the total amount of dispersate in the case where initially putting into mixer, as described above, mixing during the 2nd stirring The product of thing is smaller than the 1st time.It is therefore preferable that the mixture at least initial agitating procedure is in the scope of the product.
As mixer, various mixers can be used.Such as spiral ribbon mixer, screw mixer, high speed can be used Mix fine-graining machine, Lao Diji (Lodige) mixer, planetary stirring machine, defoaming kneader, stirring vane universal mixer, oil Paint the devices such as agitator.Particularly preferred planetary stirring machine among them.
4. the addition of binder solution and further stirring
In the preferred embodiment of the present invention, it can add binder solution after the agitating procedure and stir.It is logical Cross addition binder solution and stir, make collector foil/mixture layer interfacial adhesion of pole plate after coating, drying.
Binder solution preferably adds in the terminal stage of slurries manufacturing process, the mixing time after binder solution addition Within preferably 120 minutes.Condensed sometimes in slurries if if long agitation is carried out after adding binder solution.
As the adhesive ingredients of binder solution, butadiene-styrene rubber (SBR), nitrile rubber (NBR), butadiene rubber can be enumerated Glue (BR), Polystyrene-acrylate (St-Ac), polyacrylonitrile (PAN) etc..Preferable adhesive ingredients is SBR and St-Ac.
The usage amount of adhesive is preferably 0.1~10 mass parts relative to the dispersate of 100 mass parts, more preferably 1~5 mass parts.If adhesive is excessive, the amount of negative electrode active material is relatively reduced, therefore electrode capacity reduces, and Resistance also increases.If adhesive is very few, bond effect reduces, and when battery assembles, negative pole easily occurs in discharge and recharge Collapse, and charge and discharge circulation life reduces.
The solvent or decentralized medium of binder solution can enumerate water, alcohol (methanol, ethanol, propyl alcohol, butanol, isopropanol etc.) Deng they can be used alone or as a mixture.Wherein preferred water.
5. the characteristic of slurries
The lithium ion secondary battery negative pole slurries obtained using the above method, because the dispersates such as electrode active material are good Disperse to exist well, therefore the agglomerate of dispersate is there's almost no in slurries.
Fineness-of-grind gauge can be used to determine particle size according to JIS K5600-2-5, using the particle to measure Method that size is evaluated evaluates whether there is agglomerate.In the slurries obtained using the above method, fineness of grind is used The particle size of rule measure turns into 90% accumulation grain of the volume reference obtained using laser diffractometry of negative electrode active material Footpath (D90) is below.This means cohesion is almost not observed in slurries.
The accumulation particle diameter of volume reference, the マ Le バ for example as laser diffraction formula particle size distribution device can be used ー Application (Malvern) Mastersizer processed is determined.
In the case of using conductive auxiliary agent, its cohesion can also bring adverse effect to negative pole performance, but by using above-mentioned Method, the dispersiveness of conductive auxiliary agent also greatly improve.On the dispersiveness of conductive auxiliary agent, can use by the observation such as FE-SEM Slurries are coated on substrate and make the method for its dried state to evaluate.Use the feelings of the slurries obtained by the above method Under condition, it was observed that the state that conductive auxiliary agent disperses well.Specifically, the carbon black that average grain diameter is below 100nm is being used In the case of as conductive auxiliary agent, condense grain a diameter of less than 1 μm.
The slurries and the adaptation of collector obtained using the above method are also excellent.It is thought that due to except dispersate Beyond dispersiveness, tackifier, adhesive are also all well dispersed within the reason in slurries.Due to excellent adhesion, battery it is resistance to Long property improves.
The evaluation of adaptation, by the pole plate to being coated on collector by slurries and having dried it, measure mixture and collection The peel strength of electric body is carried out.Peel strength determines according to JIS K6854-2.
With the pole using the slurries for only adding 5% decentralized medium more than decentralized medium total amount in terminal stage and manufacturing In the case that plate is compared, using the pole plate of the slurries obtained by the above method, its adaptation greatly improves.
Adjust composition, the use level of each composition so that slurry viscosity turns into 1~10Pas, is preferably 2~5Pas.
6. the making of sheet-like cathode pole plate
Using the slurries that the above method obtains by being coated on collector and drying, lithium ion secondary battery cathode can be made Pole pole plate.
Coating of the slurries to collector can use known method to implement, and can enumerate for example using scraper, scrape rod coating Method that machine etc. is coated etc..The thickness of coating layer is usually 10~200 μm.Drying can be for example, by 70 DEG C, 1 hour It is dried in vacuo to carry out.
As collector, copper foil, aluminium foil, stainless steel foil, nickel foil, titanium foil and their Alloy Foil, carbon plate etc. can be used Known material.Among them, from intensity, electrochemical stability, cost etc., preferably copper foil, copper alloy foil.
The thickness of collector is not particularly limited, preferably 0.5~100 μm, more preferably 1~50 μm.It is strong if excessively thin Degree reduces, operational generation problem when intensity in negative material, coating.If blocked up, the current collection in battery structure The quality of body paper tinsel, the ratio of volume increase, and the energy density of battery reduces, and pellet electrode during battery making is hardened, right Winding brings obstacle.
Embodiment
Representational example is shown to the present invention below, is further elaborated with.Furthermore these examples are only used for Bright illustration, the present invention are at all not restricted to this.Furthermore the material and evaluation method used in embodiment and comparative example is as follows It is described.
(1) material
(i) negative electrode active material
Delanium：Showa Electricity work Co. Ltd. system SCMG (registration mark), D50%16 μm, D90%40 μm, compare table Area 1.6m2/g
Native graphite：China's system, D50%17 μm, D90%26 μm, specific surface area 5.9m2/g
(ii) conductive auxiliary agent
Carbon black：TIMCAL company system C65, average primary particle diameter 100nm ＞, specific surface area 65m2/g
Fibrous carbon：Showa Electricity work Co. Ltd. system VGCF-H (registration mark), average fiber footpath 150nm, fiber length 10~20nm, specific surface area 13m2/g
(iii) tackifier
Carboxymethyl cellulose (CMC)：ダ イ セ Le Off ァ イ Application ケ system Co. Ltd. system 2200
(iv) binder solution
SBR binder solutions：Japanese ゼ オ Application company systems BM-400B, 40 mass % aqueous dispersions
(2) evaluation method
(i) cohesion of negative electrode active material
The particle size in slurries is determined using fineness-of-grind gauge.Measure is carried out according to JIS K5600-2-5.The size is big Then represent that the negative electrode active material cohesion in slurries is present, it is scattered insufficient.
(ii) cohesion of conductive auxiliary agent
Use the slurries of scraper thickness of 150 μm of coating on the copper foil of 20 μm of thickness.Then, it is dried in vacuo 1 at 70 DEG C Hour, obtain the battery lead plate formed with mixture layer on copper foil.
Electrode is used to resulting battery lead plate, more than 1 μm of conductive auxiliary agent is evaluated whether there is by FE-SEM Cohesion.
(iii) peel strength
The electrode obtained using above-mentioned (ii), according to JIS K6854-2, the peel strength of measure copper foil and mixture layer.
Embodiment 1
(1) half dry-mixing is put into
To capacity 500cm3プ ラ イ ミ Network ス company system planetary stirring machines in put into 135g Delaniums, 2.84g charcoals Black and 20g the 1.1 mass %CMC aqueous solution, has been stirred 30 minutes with 30rpm blade rotary speed.
(2) stir thick
After the material for wiping the blade for being attached to planetary stirring machine off with the spatula of resin-made, enter one into the mixer The step addition 70g 1.1 mass %CMC aqueous solution, have been stirred 15 minutes with 30rpm blade rotary speed.Then, by the rotation Rotary speed is improved to 60rpm, has further been stirred 75 minutes.
(3) delay and rub
After the material for wiping the blade for being attached to planetary stirring machine off with the spatula of resin-made, enter one into the mixer The step addition 105g 1.1 mass %CMC aqueous solution, have been stirred 15 minutes with 30rpm blade rotary speed.Then, by described in Rotary speed is improved to 80rpm, has further been stirred 75 minutes.
(4) adhesive mixes
5.3g SBR binder solutions are put into the mixer, carry out water cooling while being revolved with 25rpm blade Rotary speed has stirred 15 minutes.Then, while vacuum defoamation is carried out, while having stirred 60 points with 100rpm blade rotary speed Clock, slurries are obtained.
The manufacturing condition of slurries is shown in table 1.
(5) evaluate
To slurries obtained above, confirm scattered degree based on JIS K5600-2-5 using fineness-of-grind gauge, use With the slurries of the thickness of 150 μm of scraper for coating and 1 hour electrode formed is dried in vacuo at 70 DEG C on the copper foil of 20 μm of thickness, Confirm the cohesion that whether there is more than 1 μm of conductive auxiliary agent and the peel strength based on JIS K6854-2 by FE-SEM. Evaluation result is shown in table 2.
Embodiment 2
In addition to having used 67.5g Delaniums and 67.5g native graphites instead of 135g Delaniums, carry out and reality Apply the same processing of example 1.The manufacturing condition of slurries is shown in table 1, and evaluation result is shown in table 2.
In addition, the photo shot by SEM is shown in Fig. 1.It is the enlarged drawing of native graphite particle in this, b is artificial stone The enlarged drawing of black particle, it is known that in the scattered particulate that there are carbon black such as its surface.
The evaluation photo for having used fineness-of-grind gauge is shown in Fig. 3.
Embodiment 3
In addition to replacing 2.84g carbon blacks using 2.84g fibrous carbons, processing similarly to Example 2 has been carried out.Will slurry The manufacturing condition of liquid is shown in table 1, and evaluation result is shown in into table 2.
Embodiment 4
Except replacing 135g Delaniums using 69g Delaniums and 69g native graphites, and do not add beyond carbon black, enter The processing gone similarly to Example 1.The manufacturing condition of slurries is shown in table 1, and evaluation result is shown in table 2.
Comparative example 1
(1) half dry-mixing is put into
By 67.5g Delaniums, 67.5g native graphites, 2.84g carbon blacks and the 30g 2.0 mass %CMC aqueous solution successively Input, is set to 30rpm by the rotary speed of blade and has stirred 30 minutes.
(2) stir thick
After the material for wiping the blade for being attached to planetary stirring machine off with the spatula of resin-made, additional 77g 2.0 mass % The CMC aqueous solution, after being stirred 15 minutes with 30rpm rotation number, and then rotary speed is improved to 60rpm and stirred 75 minutes.
(3) dilute
After the material for wiping the blade for being attached to planetary stirring machine off with the spatula of resin-made, additional 88g water, with 30rpm Rotary speed stir 15 minutes after, and then rotation number is improved to 80rpm and stirred 75 minutes.
(4) adhesive mixes
While input 5.3g SBR binder solutions are gone forward side by side, water-filling is cold, while being stirred 15 minutes with 25rpm rotary speed Afterwards, vacuum defoamation is carried out while being stirred 60 minutes with 100rpm rotary speed, complete slurries.
The manufacturing condition of slurries is shown in table 1, and evaluation result is shown in table 2.
Comparative example 2
(1) tackifier mixing is put into
135g Delaniums, 2.84g carbon blacks and the 195g 1.1 mass %CMC aqueous solution are put into, by the rotation speed of blade After degree is set to 30rpm stirrings 30 minutes, and then rotation number is improved to 80rpm and stirred 180 minutes.
(2) adhesive mixes
While input 5.3g SBR binder solutions are gone forward side by side, water-filling is cold, while being stirred 15 minutes with 25rpm rotary speed Afterwards, vacuum defoamation is carried out while being stirred 60 minutes with 100rpm rotary speed, complete slurries.
The manufacturing condition of slurries is shown in table 1, and evaluation result is shown in table 2.
In addition, the photo shot by SEM is shown in Fig. 2.Here, c is the ground condensed as the carbon black of conductive auxiliary agent The enlarged drawing of side, d is the enlarged drawing of native graphite particle, and e is the enlarged drawing of Delanium particle, it is known that carbon black is with 5~20 μm Size cohesion, it is scattered insufficient.
Fig. 3 will be shown in using the evaluation photo of fineness-of-grind gauge.

Claims (12)

1. a kind of manufacture method of lithium ion secondary battery negative pole slurries, has agitating procedure, the process is to containing tackifier Solution and the mixture of dispersate are stirred,
The dispersate includes negative electrode active material and conductive auxiliary agent,
The conductive auxiliary agent is 10~100nm comprising average primary particle diameter and specific surface area is 10~100m2/ g carbon black, it is averaged Fiber footpath is 5~500nm and specific surface area is 1~300m2/ g carbon fiber or its mixture,
The agitating procedure includes：Before stirring, the total amount of the negative electrode active material, the conductive auxiliary agent are put into respectively Total amount and the tackifier solution, form the weighted average α and solid constituent ratio β of the specific surface area of the dispersate product That is α × β is more than 1.3 mixture, the process being then stirred to the mixture, and does not include individually adding for starching The process of the decentralized medium of liquid or the amount of the decentralized medium individually added in the case of including the process are point in slurries Below the 5 mass % of dispersion media total amount, the weighted average α unit are m2/g。
2. the manufacture method of lithium ion secondary battery negative pole slurries according to claim 1, the agitating procedure include The process of tackifier solution and stirring is added to the dispersate and will further add tackifier solution and the behaviour stirred thereafter Make the process for carrying out 1 time or being repeated more than 2 times.
3. the manufacture method of lithium ion secondary battery negative pole slurries according to claim 2, the agitating procedure include：
The process that the total amount of the dispersate is put into mixer；With
Next, the process that the operation for putting into tackifier solution to the mixer and stirring is repeated more than 2 times.
4. the manufacture method of lithium ion secondary battery negative pole slurries according to claim 3, in initial agitating procedure The amount of the tackifier solution of middle input is 5~40 mass % of total usage amount of tackifier solution.
5. the manufacture method of lithium ion secondary battery negative pole slurries according to claim 1, the solvent of tackifier solution Include water.
6. the manufacture method of lithium ion secondary battery negative pole slurries according to claim 1, to molten containing tackifier After the process that liquid and the mixture of dispersate are stirred, there is input binder solution and the process stirred.
7. the manufacture method of lithium ion secondary battery negative pole slurries according to claim 1, the negative electrode active material It is more than a kind in non-graphite system carbon material and graphite system carbon material.
8. the manufacture method of lithium ion secondary battery negative pole slurries according to claim 1, negative electrode active material are adopted The average grain diameter D50 of the volume reference obtained with laser diffractometry is 1~50 μm.
9. the manufacture method of lithium ion secondary battery negative pole slurries according to claim 6, in described adhesive solution Contained adhesive ingredients is selected from butadiene-styrene rubber (SBR), nitrile rubber (NBR), butadiene rubber (BR), polystyrene-the third It is at least one kind of in olefin(e) acid ester (St-Ac), polyacrylonitrile (PAN) and polyamide-imides.
10. a kind of lithium ion secondary battery negative pole slurries, manufactured using the either method of claim 1~9, using grinding Levigate metric is according to the body obtained using laser diffractometry that the particle size that JIS K5600-2-5 are determined is negative electrode active material 90% accumulation particle diameter of product benchmark is below D90.
11. it is by by the lithium ion secondary battery cathode described in claim 10 a kind of lithium ion secondary battery negative pole pole plate Pole is obtained from slurries are coated on collector and are dried.
12. a kind of lithium rechargeable battery, include the lithium ion secondary battery negative pole pole plate described in claim 10 or 11.
CN201380063111.0A 2012-12-07 2013-12-06 The manufacture method of lithium ion secondary battery negative pole slurries Expired - Fee Related CN104854737B (en)

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