CN109524616A - A kind of lithium ion battery anode glue size and preparation method thereof - Google Patents
A kind of lithium ion battery anode glue size and preparation method thereof Download PDFInfo
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- CN109524616A CN109524616A CN201811291412.XA CN201811291412A CN109524616A CN 109524616 A CN109524616 A CN 109524616A CN 201811291412 A CN201811291412 A CN 201811291412A CN 109524616 A CN109524616 A CN 109524616A
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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
- H01M4/04—Processes of manufacture in general
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- 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
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- Y02E60/10—Energy storage using batteries
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Abstract
The present invention relates to a kind of lithium ion battery anode glue sizes and preparation method thereof, belong to technical field of lithium ion.The preparation method of lithium ion battery anode glue size of the invention, comprising the following steps: 1) glue is added in electrocondution slurry and mixes, composite mortar is made；The glue includes binder and solvent；The electrocondution slurry includes conductive agent and dispersing agent；2) part positive active material is added in gained composite mortar and is mixed, obtain primary anode sizing agent；3) remaining positive active material is added in primary anode sizing agent mix to get.The slurry that the preparation method of lithium ion battery anode glue size of the invention obtains is uniformly dispersed, stablizes and helps to improve lithium ion cell positive energy density, it is observed through scanning electron microscope, reunite between particle without obvious in anode sizing agent obtained, conductive agent is uniformly coated on positive active material.
Description
Technical field
The present invention relates to a kind of lithium ion battery anode glue sizes and preparation method thereof, belong to technical field of lithium ion.
Background technique
The advantages that lithium ion battery is with its high working voltage, high-energy density, long circulation life, safety and environmental protection, always with
Come in consumer electronics product and power category product by very big attention.As the function of battery consumption class product is gradually strong
Greatly, also increasing for the demand of battery capacity, therefore can be increasing for the lithium ion battery demand of high-energy density.
When preparing lithium ion cell positive, the uniformity coefficient and stability of anode sizing agent are for performance of lithium ion battery
Performance has very important influence.The preparation method of anode sizing agent is more in the prior art, as application publication number is
The Chinese invention patent application of CN107732242A discloses a kind of preparation method of lithium ion battery anode glue size, and this method is
Carbon nano tube paste and graphene slurry are subjected to mixing dispersion, conductive agent slurry is made；Binder is uniform with stirring solvent
Glue is made；Then part positive active material, conductive agent slurry and glue are mixed, primary anode sizing agent is made；Again
Remaining positive active material is added in primary anode sizing agent, is stirred evenly, solid content is adjusted.The preparation side of the anode sizing agent
Method mixes part positive active material, conductive agent and glue simultaneously, and this pulping way is unfavorable for conductive agent and bonding
Agent is in the dispersion of anode sizing agent, and the stability of gained slurry is also poor.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of lithium ion battery anode glue size, can be improved point of conductive agent
It dissipates uniformity coefficient and improves the stability of anode sizing agent.
The present invention also provides a kind of above-mentioned preparation methods, and lithium ion battery anode glue size is made.
In order to achieve the goal above, technical solution used by the preparation method of lithium ion battery anode glue size of the invention
It is:
A kind of preparation method of lithium ion battery anode glue size, comprising the following steps:
1) glue is added in electrocondution slurry and is mixed, composite mortar is made；The glue includes binder and solvent；It is described
Electrocondution slurry includes conductive agent and dispersing agent；
2) part positive active material is added in gained composite mortar and is mixed, obtain primary anode sizing agent；
3) remaining positive active material is added in primary anode sizing agent mix to get.
The preparation method of lithium ion battery anode glue size of the invention, by conductive agent, binder, active material with suitable
Ratio, the slurry obtained after the mixing of suitable pulping process are uniformly dispersed, stablize and help to improve lithium ion cell positive
Energy density.It observes, reunites between particle without obvious in anode sizing agent obtained, conductive agent is uniform through scanning electron microscope
It is coated on positive active material.The preparation method of lithium ion battery anode glue size of the invention, processing step is simple to operation,
It is suitble to industrialized production.
Preferably, the solid content of the glue is 5~14%.
Preferably, the solid content of the electrocondution slurry is 0.1~10%.It is further preferred that the electrocondution slurry is consolidated
Content is 2~5%.
Preferably, in step 2), the quality for the positive active material being added in composite mortar is that positive active material is total
The 45~55% of quality.It is further preferred that the quality for the positive active material being added in composite mortar is positive electrode active material
The 50% of matter gross mass.
Preferably, the solid content of the lithium ion battery anode glue size is 60~78%.Control the solids of anode sizing agent
Content can make slurry have uniform and stable characteristic, 60~78% convenient for the progress of painting work.It is further preferred that institute
The solid content for stating lithium ion battery anode glue size is 60~72%.
Preferably, the conductive agent is at least one of carbon nanotube, conductive black.Preferably, the pipe of carbon nanotube
Diameter is 0.5~80nm, 1~10 μm of pipe range.It is further preferred that the caliber of carbon nanotube is 0.5~60nnm.Conductive black
Partial size is 25~200nm, and specific surface area is 50~300m2/g。
In the lithium ion battery anode glue size, the total weight number of positive active material, conductive agent and binder is with 100
Part meter, positive active material is 97~98.5 parts, conductive agent is 0.1~1.5 part, binder is 0.5~1.5 part.
Preferably, the average grain diameter of the positive active material is 3~20 μm.
Preferably, the positive active material is tertiary cathode material.It is further preferred that the positive active material is
LiNixMnyCozO2,0.5≤x < 1.0,0 < y < 0.5, z > 0, x+y+z=1.0.
Preferably, the solvent is N-Methyl pyrrolidone.
Preferably, the dispersing agent is N-Methyl pyrrolidone.
Preferably, in step 2) and step 3), the mixing is all made of shear-mixed, and the linear velocity of shear-mixed is 2~
30m/s。
The shear-mixed carries out in double-planet mixing apparatus, and the revolution speed of shear-mixed is 20~40r/min.
Preferably, in step 3), remaining positive active material is added in primary anode sizing agent after mixing, is added in system
The viscosity for entering solvent adjustment slurry is 4000~9000mPas.It is further preferred that adjusting slurry after solvent is added in system
The viscosity of material is 5000~6500mPas.
Technical solution used by lithium ion battery anode glue size of the invention are as follows:
Lithium ion battery anode glue size made from a kind of preparation method using above-mentioned lithium ion battery anode glue size.
Lithium ion battery anode glue size of the invention is with good stability and uniformity.
Detailed description of the invention
Fig. 1 is the SEM figure of the lithium ion battery anode glue size in embodiment 1；
Fig. 2 is the SEM figure of the lithium ion battery anode glue size in comparative example 1；
Fig. 3 is the SEM figure of the lithium ion battery anode glue size in comparative example 2.
Specific embodiment
Below in conjunction with specific embodiment, further description of the technical solution of the present invention.
In specific embodiment, the specific surface of used conductive black is 50~300m2/ g, used tertiary cathode
Material is LiNi0.6Mn0.2Co0.2O2；Used multi-walled carbon nanotube slurry and single-walled carbon nanotube slurry are by multi wall respectively
Carbon nanotube, single-walled carbon nanotube are dispersed in obtained in N-Methyl pyrrolidone.
Embodiment 1
The lithium ion battery anode glue size of the present embodiment, mainly by the component of N-Methyl pyrrolidone and following parts by weight
Composition: 97 parts of tertiary cathode material, 1.5 parts of multi-walled carbon nanotube, 1.5 parts of Su Wei PVDF5130 binder；Tertiary cathode material
Average grain diameter be 3 μm；The solid content of lithium ion battery anode glue size is 72%.
The preparation method of the lithium ion battery anode glue size of the present embodiment, comprising the following steps:
1) Su Wei PVDF5130 binder and N-Methyl pyrrolidone are added in high speed disperser, disperse Su Wei after 4h
The dissolution of PVDF5130 binder finishes, and obtains the glue that solid content is 10%；
2) gained glue is added in electrocondution slurry in double-planet mixing apparatus with the linear velocity shear-mixed of 10m/s
2.5h obtains composite mortar；Electrocondution slurry is the multi-walled carbon nanotube slurry that solid content is 5% (quality), multi wall carbon in slurry
The caliber of nanotube is 5~11nm, and length is 1~5 μm；
3) by the tertiary cathode material of 50% (quality) be added in the composite mortar in double-planet mixing apparatus with
The linear velocity of 0.3m/s is sheared, and the revolution speed mixing 0.5h of 30r/min obtains primary anode sizing agent；
4) tertiary cathode material of remaining 50% (quality) is added in the primary anode sizing agent of gained and is continued with 30r/min's
Revolution speed, the linear velocity shear-mixed 2.5h of 10m/s, it is 6000- that N-Methyl pyrrolidone adjustment viscosity, which is then added,
6500mPas to get.
Embodiment 2
The lithium ion battery anode glue size of the present embodiment, mainly by the component of N-Methyl pyrrolidone and following parts by weight
Composition: 97 parts of tertiary cathode material, 1 part of conductive black, 0.5 part of multi-walled carbon nanotube, 1.5 parts of Su Wei PVDF5130 binder；
The average grain diameter of tertiary cathode material is 20 μm；The average grain diameter of conductive black is 25nm；Lithium ion battery anode glue size is consolidated
Content is 72%.
The preparation method of the lithium ion battery anode glue size of the present embodiment, comprising the following steps:
1) Su Wei PVDF5130 binder and N-Methyl pyrrolidone are added in high speed disperser, disperse Su Wei after 4h
The dissolution of PVDF5130 binder finishes, and obtains the glue that solid content is 10%；
Conductive black is added in multi-walled carbon nanotube slurry, and suitable N-Methyl pyrrolidone is added, in double-planet
With the linear velocity shear-mixed 2h of 10m/s in mixing apparatus, the electrocondution slurry that solid content is 10% is obtained；Multi-walled carbon nanotube slurry
The solid content of material is 5% (quality), and the caliber of multi-walled carbon nanotube is 5~11nm in slurry, and length is 1~5 μm；
2) gained glue is added in electrocondution slurry in double-planet mixing apparatus with the linear velocity shear-mixed of 10m/s
2.5h obtains composite mortar；
3) by the tertiary cathode material of 50% (quality) be added in the composite mortar in double-planet mixing apparatus with
The linear velocity of 0.3m/s is sheared, and the revolution speed mixing 0.5h of 30r/min obtains primary anode sizing agent；
4) tertiary cathode material of remaining 50% (quality) is added in the primary anode sizing agent of gained and is continued with 30r/min's
Revolution speed, the linear velocity shear-mixed 2.5h of 10m/s, it is 6000- that N-Methyl pyrrolidone adjustment viscosity, which is then added,
6500mPas to get.
Embodiment 3
The lithium ion battery anode glue size of the present embodiment, mainly by the component of N-Methyl pyrrolidone and following parts by weight
Composition: 97.5 parts of tertiary cathode material, 0.9 part of conductive black, 0.1 part of single-walled carbon nanotube, Su Wei PVDF5130 binder 1.5
Part；The average grain diameter of tertiary cathode material is 12 μm；The average grain diameter of conductive black is 200nm；Lithium ion battery anode glue size
Solid content be 72%.
The preparation method of the lithium ion battery anode glue size of the present embodiment, comprising the following steps:
1) Su Wei PVDF5130 binder and N-Methyl pyrrolidone are added in high speed disperser, disperse Su Wei after 4h
The dissolution of PVDF5130 binder finishes, and obtains the glue that solid content is 9%；
Conductive black is added in single-walled carbon nanotube slurry, is cut in double-planet mixing apparatus with the linear velocity of 10m/s
Mixing 2h is cut, the electrocondution slurry that solid content is 2% is obtained；Single-walled carbon nanotube slurry solid content is 0.4% (quality), in slurry
The caliber of single-walled carbon nanotube is less than 1nm, and length is 5~10 μm；
2) gained glue is added in electrocondution slurry in double-planet mixing apparatus with the linear velocity shear-mixed of 10m/s
2.5h obtains composite mortar；
3) by the tertiary cathode material of 50% (quality) be added in the composite mortar in double-planet mixing apparatus with
The revolution speed of 30r/min, the linear velocity shearing of 0.3m/s, the revolution speed mixing 0.5h of 30r/min obtain primary anode slurry
Material；
4) tertiary cathode material of remaining 50% (quality) is added in the primary anode sizing agent of gained and is continued with 30r/min's
Revolution speed, the linear velocity shear-mixed 2.5h of 30m/s, it is 6000- that N-Methyl pyrrolidone adjustment viscosity, which is then added,
6500mPas to get.
Embodiment 4
The lithium ion battery anode glue size of the present embodiment, mainly by the component of N-Methyl pyrrolidone and following parts by weight
Composition: 98.5 parts of tertiary cathode material, 0.1 part of single-walled carbon nanotube, 1.4 parts of Su Wei PVDF5130 binder；Tertiary cathode material
The average grain diameter of material is 8 μm；The solid content of lithium ion battery anode glue size is 60%.
The preparation method of the lithium ion battery anode glue size of the present embodiment, comprising the following steps:
1) PVDF5130 binder and N-Methyl pyrrolidone are added in high speed disperser, disperse Su Wei after 4h
The dissolution of PVDF5130 binder finishes, and obtains the glue that solid content is 5%；
2) gained glue is added in electrocondution slurry in double-planet mixing apparatus with the linear velocity shear-mixed of 10m/s
2.5h obtains composite mortar；Electrocondution slurry is the single-walled carbon nanotube slurry that solid content is 5% (quality), single-walled carbon nanotube slurry
In material, the caliber of single-walled carbon nanotube is 30~60nm, and length is 1~5 μm；
3) by the tertiary cathode material of 55% (quality) be added in the composite mortar in double-planet mixing apparatus with
The revolution speed of 20r/min, the linear velocity shear-mixed 0.5h of 2m/s, obtains primary anode sizing agent；
4) tertiary cathode material of remaining 45% (quality) is added in the primary anode sizing agent of gained and is continued with 40r/min's
Revolution speed, the linear velocity shear-mixed 2.5h of 2m/s, it is 4000mPas that N-Methyl pyrrolidone adjustment viscosity, which is then added,
To obtain the final product.
Comparative example 1
The composition and solid content of the lithium ion battery anode glue size of comparative example 1 are the same as embodiment 1.
Lithium ion battery anode glue size in the preparation method and embodiment 1 of the lithium ion battery anode glue size of comparative example 1
Preparation method the difference is that: in comparative example 1 step 2) be will electrocondution slurry be added glue in carry out dispersion be made it is compound
Slurry.
Comparative example 2
The anode sizing agent of the lithium ion battery anode glue size of comparative example, composition and preparation method and embodiment 1 is essentially identical,
Difference, which is only that, becomes 60% using by the solid contents in embodiment 1.
Experimental example
This experimental example using scanning electron microscope to the lithium ion battery anode glue size of embodiment 1 and comparative example 1~2 into
The observation of row surface topography, as shown in Figure 1, 2, 3.
In Fig. 1, carbon nanotube is uniformly coated in ternary material particle surface, and in Fig. 2 and Fig. 3, carbon nanotube is in ternary
The surface of material granule is uneven in cladding, and a large amount of reunite occurs in the carbon nanotube in Fig. 3.Suitable charging sequence and suitable
Solid content control be conductive agent is evenly dispersed in embodiment 1 internal cause, relative to conductive agent in comparative example 1 and comparative example 2
The lithium ion battery anode glue size stability of uneven dispersion situation, embodiment 1 is convenient for following process well, is conducive to be coated with pole piece
Consistency.
Claims (10)
1. a kind of preparation method of lithium ion battery anode glue size, it is characterised in that: the following steps are included:
1) glue is added in electrocondution slurry and is mixed, composite mortar is made；The glue includes binder and solvent；The conduction
Slurry includes conductive agent and dispersing agent；
2) part positive active material is added in gained composite mortar and is mixed, obtain primary anode sizing agent；
3) remaining positive active material is added in primary anode sizing agent mix to get.
2. the preparation method of lithium ion battery anode glue size according to claim 1, it is characterised in that: the glue is consolidated
Content is 5~14%.
3. the preparation method of lithium ion battery anode glue size according to claim 1, it is characterised in that: the electrocondution slurry
Solid content be 0.1~10%.
4. the preparation method of lithium ion battery anode glue size according to claim 1, it is characterised in that: in step 2),
The quality for the positive active material being added in composite mortar is the 45~55% of positive active material gross mass.
5. the preparation method of lithium ion battery anode glue size according to claim 1, it is characterised in that: the lithium-ion electric
The solid content of pond anode sizing agent is 60~78%.
6. the preparation method of lithium ion battery anode glue size according to claim 1, it is characterised in that: the conductive agent is
At least one of carbon nanotube, conductive black.
7. the preparation method of lithium ion battery anode glue size according to claim 1, it is characterised in that: the lithium-ion electric
In the anode sizing agent of pond, in terms of 100 parts, positive active material is the total weight number of positive active material, conductive agent and binder
97~98.5 parts, conductive agent be 0.1~1.5 part, binder is 0.5~1.5 part.
8. the preparation method of lithium ion battery anode glue size according to claim 1, it is characterised in that: the positive-active
Substance is tertiary cathode material.
9. the preparation method of lithium ion battery anode glue size according to claim 1, it is characterised in that: step 2) and step
3) in, the mixing is all made of shear-mixed, and the linear velocity of shear-mixed is 2~30m/s.
10. lithium ion cell positive made from a kind of preparation method of lithium ion battery anode glue size as described in claim 1
Slurry.
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| CN111883736A (en) * | 2020-06-08 | 2020-11-03 | 惠州锂威新能源科技有限公司 | Preparation method of lithium ion battery anode slurry |
| CN112186140A (en) * | 2019-07-04 | 2021-01-05 | 江苏天奈科技股份有限公司 | Silicon-based active composite conductive slurry applied to silicon-carbon cathode and cathode slurry mixing method |
| CN114864871A (en) * | 2022-03-31 | 2022-08-05 | 湖北亿纬动力有限公司 | Positive electrode slurry and preparation method and application thereof |
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Application publication date: 20190326 |