CN105119000B - The aqueous PVDF slurries and its preparation, application method of a kind of lithium ion battery - Google Patents
The aqueous PVDF slurries and its preparation, application method of a kind of lithium ion battery Download PDFInfo
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- CN105119000B CN105119000B CN201510452494.1A CN201510452494A CN105119000B CN 105119000 B CN105119000 B CN 105119000B CN 201510452494 A CN201510452494 A CN 201510452494A CN 105119000 B CN105119000 B CN 105119000B
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- lithium ion
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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
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses the aqueous PVDF slurries and its preparation, application method of a kind of lithium ion battery, aim to provide a kind of dispersion effect good, the aqueous PVDF slurries of the small lithium ion battery of environmental pollution, technical points, the aqueous PVDF slurries are calculated by gross mass 100%, the mass percent of each component is, PVDF powders 0.05% 20%, dispersant 0.1% 10%, wetting agent 0.2% 5%, and surplus is water；Belong to technical field of lithium batteries.
Description
Technical field
It is a kind of the aqueous of lithium ion battery specifically the present invention relates to a kind of slurry of lithium ion battery
PVDF slurries, belong to technical field of lithium batteries.
Background technology
Lithium ion cell positives all at present is all to dissolve PVDF or PVDF+HFP mixtures with NMP organic solvents, so
Add conductive agent again afterwards.Organic solvent PVDF is volatile and burns, and has dense smell, healthy to employee harmful.Together
When NMP need expensive equipment to reclaim, and consume substantial amounts of electric energy, do not utilize and save the energy and reduce cost.The present invention is used
Aqueous solvent replaces organic solvent NMP, on the one hand reduction temperature and energy consumption, on the other hand improves employee's operating environment, especially right
The environmental impact assessment of lithium battery, which is brought, significantly to be improved and improves.
Chinese patent CN201210273419.5 provides a kind of for preparing (containing lithium ion) electrochemical cell electrode
Slurry, the slurry be included in aqueous solution in polyacrylic acid (PAA), carboxymethyl cellulose (CMC), butadiene-styrene rubber
(SBR) combination of at least three and in polyvinylidene fluoride (PVDF), and can electrochemical activation compound.But the skill
Disperseing PVDF in art scheme with PAA, CMC and water is difficult, it is impossible to be distributed to well-proportioned degree, it is easy to reunites and divides
Layer, it is also difficult to the scattered positive active material such as material such as cobalt acid lithium, LiFePO4 and ternary.And application CMC and PAA etc. is aqueous
Glue, if positive pole is current high-tension cobalt acid lithium, special cell voltage is 4.35V, 4.4V or higher 4.5V, then negative electrode pair
Lithium current potential is up to 4.7V in full charging, it is easy to the water-base cement such as oxidation Decomposition CMC, can deteriorate the performance of battery, particularly circulate
And high-temperature storage, so can be used only in negative pole system to CMC and SBR system at present.
Chinese patent CN201410445356.6 provides a kind of ceramics and the lithium battery diaphragm of gelatin polymer MULTILAYER COMPOSITE
And preparation method thereof, it is characterized in that, using deionized water as solvent, Water-soluble adhesive, surfactant, disperses
Agent, thickener add stirring and dissolving, wiring solution-forming in deionized water in normal temperature；Polymer powder particle is added, is stirred,
It is made into water paste；Containing 0.1%~2% water soluble polymer thickener in slurry, 0.01%~2% aqueous dispersion,
0.01%~1% surfactant, 0.1%~5% Aqueous Adhesives, 5%~25% polymer powder particle, 67%
~83% deionized water, above-mentioned is all mass fraction；The weight average molecular weight of polymer powder particle is 12-16 ten thousand, and particle diameter is
100-300nm；The technical scheme major amount dispersed ceramic powder is still aqueous molten using CMC etc., it is necessary to be applied on barrier film
Agent, has negative effect in high-tension positive pole to the high temperature and cycle life of battery, and the latter is aqueous without CMC etc.
Glue, thus to battery, particularly high-tension high energy density cells have no adverse effect.
The content of the invention
In view of the above-mentioned problems, environmental pollution small lithium ion battery good it is an object of the invention to provide a kind of dispersion effect
Aqueous PVDF slurries, to prepare the aqueous PVDF slurries, the present invention also has a technical scheme to be to provide the aqueous PVDF
The preparation method of slurry.
Therefore, the previous technical scheme that the present invention is provided is such：
A kind of aqueous PVDF slurries of lithium ion battery, are calculated, the mass percent of each component by gross mass 100%
For, PVDF powders 0.05%-20%, dispersant 0.1%-10%, wetting agent 0.2%-5%, surplus is water；
Further, the aqueous PVDF slurries of above-mentioned lithium ion battery, the dispersant is calculated by gross mass 100%,
It is made up of 10%-50% epiphyte hydrophobic proteins, 8%-40% glycols, 5%-30% silica-based surfactants.
The aqueous PVDF slurries of above-mentioned lithium ion battery, the aqueous PVDF slurries solid content of the lithium ion battery
For 0.05-20%.
Further, the aqueous PVDF slurries of above-mentioned lithium ion battery, the wetting agent is double (propionitrile) ethers of ethylene glycol.
Further, the aqueous PVDF slurries of above-mentioned lithium ion battery.
Further, the aqueous PVDF slurries of above-mentioned lithium ion battery, the glycols is enediol.
Further, the aqueous PVDF slurries of above-mentioned lithium ion battery, the glycols is acetylenic glycols.
Further, the aqueous PVDF slurries of above-mentioned lithium ion battery, the structural formula of the silica-based surfactant is such as
Under：
R is alkyl.
The latter technique scheme of the present invention is to provide the preparation method of the aqueous PVDF slurries of described lithium ion battery,
Comprise the steps successively：
1) each component is weighed according to the mass percent described in claim 1；
2) by step 1) dispersant that weighs adds into water, stirs 10 minutes, obtain mixed liquor A；
3) step 1 is added into mixed liquor A) the PVDF powder stirrings that weigh 10 minutes, obtain mixed liquid B；
4) step 1 is added into mixed liquid B) wetting agent that weighs, stirring 30min can obtain.
Last technical scheme of the present invention, is to provide the user of the aqueous PVDF slurries of the lithium ion battery
Method, this method comprises the steps successively：
1) 1%-5% conductive agents are added in the aqueous PVDF slurries described in claim 1, at normal temperatures with stirring；
2) to step 1) in add active material and make its solid content in 90-96%, stir 120min；Add 0.05% second two
Alcohol defoamer, you can be applied on aluminium foil, is then dried, and makes battery core.
Compared with prior art, the technical scheme that the present invention is provided has following technological merit：
1st, hydrophobic and hydrophilic double property bases are contained in present invention application active dispersing agents and wetting agent, special active dispersing agents
Group, in PVDF particle surfaces formation hydrophilic radical, is easy to PVDF to disperse or dissolve in aqueous solvent well.
2nd, the present invention is without CMC and SBR water-base cements, with some lower boiling surfactants, because of height in positive pole coating
Temperature baking is lower to volatilize, and does not end up in positive pole.Meanwhile, the dispersant and wetting agent added in the present invention is to the conductive agent in positive pole
Such as CNT and graphene have extraordinary dispersion effect, to active material such as cobalt acid lithium, LiFePO4, the ternary of positive pole
Also there is good peptizaiton Deng inorganic particle powder, be easy to be coated into uniform, stable anode pole piece, the circulation to battery
Life-span and high rate performance improve a lot.
Brief description of the drawings
Fig. 1 is circulating battery curve map prepared by the aqueous PVDF slurries that the present invention is provided；
Fig. 2 is battery different multiplying discharge performance prepared by the aqueous PVDF slurries that the present invention is provided.
Embodiment
The present invention is further illustrated below by the mode of embodiment, but does not constitute any limitation of the invention, is appointed
The modification for the limited number of time that who is made in scope of the presently claimed invention is still in scope of the presently claimed invention.
Embodiment 1
The aqueous PVDF slurries for another lithium ion battery that the present invention is provided, its solid content is 1%；Per 100g slurries
In the mass percent of each component be, double (propionitrile) ethers of PVDF powders 20g, epiphyte hydrophobic protein HFBI 10g, ethylene glycol
0.2g, surplus is water.
Embodiment 2
The aqueous PVDF slurries for another lithium ion battery that the present invention is provided, its solid content is 7%；Per 100g slurries
In the mass percent of each component be, double (propionitrile) ethers of PVDF powders 0.05g, epiphyte hydrophobic protein HFBII1g, ethylene glycol
5g, surplus is water.
Embodiment 3
The aqueous PVDF slurries for another lithium ion battery that the present invention is provided, its solid content is 5%；Per 100g slurries
In the mass percent of each component be, double (propionitrile) the ether 3g of PVDF powders 10g, Isosorbide-5-Nitrae-butylene glycol 50g, ethylene glycol, surplus
For water.
Embodiment 4
The aqueous PVDF slurries for another lithium ion battery that the present invention is provided, its solid content is 20%；The slurry per 100g
The mass percent of the component of each in material is, double (propionitrile) the ether 1g of PVDF powders 12g, butynediols 0.1g, ethylene glycol, and surplus is
Water.
Embodiment 5
The aqueous PVDF slurries for another lithium ion battery that the present invention is provided, its solid content is 12%；The slurry per 100g
The mass percent of the component of each in material is, PVDF powders 8g, epiphyte hydrophobic protein HFBI types 1g, butynediols 1g, ethylene glycol
Double (propionitrile) ether 1g, surplus is water.
Embodiment 6
The aqueous PVDF slurries for another lithium ion battery that the present invention is provided, its solid content is 18%；The slurry per 100g
The mass percent of the component of each in material is, PVDF powders 16g, epiphyte hydrophobic protein HFBI types 1g, Isosorbide-5-Nitrae-butylene glycol 0.8g,0.6g, double (propionitrile) the ether 3g of ethylene glycol, surplus is water.
Its preparation method is：
1) each component is weighed by any one group of mass number in embodiment 1 to 6；
2) by step 1) dispersant that weighs adds into water, stirs 10 minutes, obtain mixed liquor A；
3) step 1 is added into mixed liquor A) the PVDF powders that weigh, stir 10 minutes, obtain mixed liquid B；
4) step 1 is added into mixed liquid B) double (propionitrile) ethers of the ethylene glycol that weighs, stirring 30min can obtain.
The application method of the aqueous PVDF slurries of the lithium ion battery, comprises the steps successively：
1) will in above-mentioned aqueous PVDF slurries add 1g-5g conductive agents, at normal temperatures to stir 20min, after
5000r/min is lower at a high speed to stir 30min；
2) to step 1) in add active material (material such as sour lithium, LiFePO4, ternary) its solid content is arrived 90
120min is stirred under 96%, 3000r/min；Add 0.05g ethylene glycol defoamers, you can be applied on aluminium foil, then dry, make
Make battery core.
It should be noted that the aqueous PVDF slurries that the present invention is provided, routinely contain admittedly in practical application according to this area
Amount is required, is diluted with water to solid content 1% to 3.5%, is being carried out aforesaid operations.
The high temperature storage data that the battery prepared using the aqueous PVDF slurries of the present invention makes battery are as follows：
As it can be seen from table 1 the battery that the aqueous PVDF slurries provided with the present invention are made, 85 DEG C of full electricity are stored 4 hours
Thickness only increases less than 5%, capacity restoration rate to more than 95%.As can be seen from Figure 1 the capacity of 300 times also 90% is recycled to, than
The 80% of current industry requirement is high.Figure it is seen that 5C multiplying powers release more than 90% capacity, these are enough
The battery that the aqueous PVDF slurries that the bright application present invention is provided are made, bonding is uniform, firm, and interface stability, high-temperature behavior is good.
Battery prepared by the aqueous PVDF slurries provided using the present invention, cyclicity can be seen that by table 1, Fig. 1, Fig. 2
Energy, discharge performance are good.
Claims (8)
1. the aqueous PVDF slurries of a kind of lithium ion battery, it is characterised in that calculated by gross mass 100%, each component
Mass percent is, PVDF powders 0.05%-20%, dispersant 0.1%-10%, wetting agent 0.2%-5%, and surplus is water；
The dispersant is calculated by gross mass 100%, by 10%-50% epiphyte hydrophobic proteins, 8%-40% glycols, 5%-
30% silica-based surfactant is constituted.
2. the aqueous PVDF slurries of lithium ion battery according to claim 1, it is characterised in that the lithium ion battery
Aqueous PVDF slurries solid content is 0.05-20%.
3. the aqueous PVDF slurries of lithium ion battery according to claim 1, it is characterised in that the wetting agent is second
Double (propionitrile) ethers of glycol.
4. the aqueous PVDF slurries of lithium ion battery according to claim 1, it is characterised in that the glycols is alkene
Glycol.
5. the aqueous PVDF slurries of lithium ion battery according to claim 1, it is characterised in that the glycols is alkynes
Glycol.
6. the aqueous PVDF slurries of lithium ion battery according to claim 1, it is characterised in that the silicon substrate surface is lived
The structural formula of property agent is as follows：
R is alkyl.
7. prepare the aqueous PVDF slurries of the lithium ion battery described in claim 1, it is characterised in that successively including following steps
Suddenly：
1) mass percent as described in claim 1 weighs each component；
2) by step 1) dispersant that weighs adds into water, stirs 8-12 minutes, obtain mixed liquor A；
3) step 1 is added into mixed liquor A) the PVDF powder stirrings that weigh 8-12 minutes, obtain mixed liquid B；
4) step 1 is added into mixed liquid B) wetting agent that weighs, stir and evenly mix and produce.
8. the application method of the aqueous PVDF slurries of the lithium ion battery described in claim 1, it is characterised in that include successively
Following step：
1) 1%-5% conductive agents are added into the aqueous PVDF slurries described in claim 1, at normal temperatures with stirring；
2) to step 1) in add active material and make its solid content in 90-96%, stir 120min；0.05% ethylene glycol is added to disappear
Infusion, you can be applied on aluminium foil, is then dried, and makes battery core.
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| CN109037551A (en) * | 2018-08-01 | 2018-12-18 | 河北金力新能源科技股份有限公司 | A kind of lithium ion battery separator and preparation method thereof |
| CN109449354A (en) * | 2018-10-25 | 2019-03-08 | 东莞东阳光科研发有限公司 | Ceramic slurry, Ceramic Composite diaphragm and lithium ion battery |
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| CN103746085A (en) * | 2013-11-07 | 2014-04-23 | 深圳市星源材质科技股份有限公司 | Coating composite separation membrane and preparation method thereof |
| CN103915595A (en) * | 2014-04-23 | 2014-07-09 | 深圳市星源材质科技股份有限公司 | Aqueous polymer diaphragm and preparation method thereof |
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| PL2436067T3 (en) * | 2009-05-29 | 2018-11-30 | Arkema Inc. | Aqueous polyvinylidene fluoride composition |
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| CN103746085A (en) * | 2013-11-07 | 2014-04-23 | 深圳市星源材质科技股份有限公司 | Coating composite separation membrane and preparation method thereof |
| CN103915595A (en) * | 2014-04-23 | 2014-07-09 | 深圳市星源材质科技股份有限公司 | Aqueous polymer diaphragm and preparation method thereof |
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