CN105119000A - Aqueous PVDF slurry for lithium ion battery and its preparation method and use method - Google Patents
Aqueous PVDF slurry for lithium ion battery and its preparation method and use method Download PDFInfo
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- CN105119000A CN105119000A CN201510452494.1A CN201510452494A CN105119000A CN 105119000 A CN105119000 A CN 105119000A CN 201510452494 A CN201510452494 A CN 201510452494A CN 105119000 A CN105119000 A CN 105119000A
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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
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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses aqueous PVDF slurry for a lithium ion battery and its preparation method and use method. The aqueous PVDF slurry for a lithium ion battery has good dispersion effects and small environmental pollution. The aqueous PVDF slurry comprises, by mass, 0.05-20% of PVDF powder, 0.1-10% of a dispersant, 0.2-5% of a wetting agent and the balance water and belongs to the field of a lithium ion battery technology.
Description
Technical field
The present invention relates to a kind of slurry of lithium ion battery, specifically, be a kind of water-based PVDF slurry of lithium ion battery, belong to technical field of lithium batteries.
Background technology
Lithium ion cell positives all is at present all with NMP organic solvent dissolution PVDF or PVDF+HFP mixture, and then adds conductive agent.Organic solvent PVDF is volatile and burn, and has dense smell, healthy harmful to employee.NMP needs very expensive equipment to reclaim simultaneously, and consumes a large amount of electric energy, does not utilize energy savings and reduces costs.Use solvent of the present invention replaces organic solvent NMP, reduces temperature and energy consumption on the one hand, improves employee's operating environment on the other hand, brings especially improve significantly and improve the environmental impact assessment of lithium battery.
Chinese patent CN201210273419.5 provides a kind of slurry for the preparation of (containing lithium ion) electrochemical cell electrode, described pulp bales is contained in the combination of at least three in polyacrylic acid (PAA), carboxymethyl cellulose (CMC), butadiene-styrene rubber (SBR) and the polyvinylidene fluoride (PVDF) in aqueous solution, and can the compound of electrochemical activation.But disperse PVDF to be very difficult with PAA, CMC and water in this technical scheme, well-proportioned degree can not be distributed to, be easy to reunite and layering, be also difficult to dispersion positive active material as materials such as cobalt acid lithium, LiFePO4 and ternarys.And apply the water-base cements such as CMC and PAA, if positive pole is current high-tension cobalt acid lithium, special cell voltage is 4.35V, 4.4V or higher 4.5V, so negative electrode to lithium current potential at full charging up to 4.7V, be easy to the water-base cements such as oxidation Decomposition CMC, the performance of battery can be worsened, particularly circulation and high-temperature storage, so negative pole system can only be used in CMC and SBR system at present.
Chinese patent CN201410445356.6 provides lithium battery diaphragm of a kind of pottery and gelatin polymer MULTILAYER COMPOSITE and preparation method thereof, its technical essential is, using deionized water as solvent, Water-soluble adhesive, surfactant, dispersant, thickener are added deionized water for stirring at normal temperature and dissolve, wiring solution-forming; Add polymer powder particle again, stir, be made into water paste; Containing the water soluble polymer thickener of 0.1% ~ 2% in slurry, the aqueous dispersion of 0.01% ~ 2%, the surfactant of 0.01% ~ 1%, the Aqueous Adhesives of 0.1% ~ 5%, the polymer powder particle of 5% ~ 25%, the deionized water of 67% ~ 83%, 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; This technical scheme major amount dispersed ceramic powder, need to be applied on barrier film, still the aqueous solvents such as CMC are used, negative effect is had to the high temperature of battery and cycle life in high-tension positive pole uses, and the latter is not containing water-base cements such as CMC, thus to battery, particularly high-tension high energy density cells does not have negative effect.
Summary of the invention
For the problems referred to above, the object of this invention is to provide a kind of dispersion effect good, the water-based PVDF slurry of the lithium ion battery that environmental pollution is little, for preparing this water-based PVDF slurry, the present invention also has a technical scheme to be to provide the preparation method of this water-based PVDF slurry.
For this reason, previous technical scheme provided by the invention is such:
A water-based PVDF slurry for lithium ion battery, calculates by gross mass 100%, and the mass percent of each component is, PVDF powder 0.05%-20%, dispersant 0.1%-10%, wetting agent 0.2%-5%, and surplus is water.
The water-based PVDF slurry of above-mentioned lithium ion battery, the water-based PVDF slurry solid content of described lithium ion battery is 0.05-20%.
Further, the water-based PVDF slurry of above-mentioned lithium ion battery, described wetting agent is ethylene glycol bis (propionitrile) ether.
Further, the water-based PVDF slurry of above-mentioned lithium ion battery, described dispersant is one of them or combination in any of epiphyte hydrophobic protein or glycols or silica-based surfactant.
Further, the water-based PVDF slurry of above-mentioned lithium ion battery, described dispersant calculates by gross mass 100%, is made up of 10%-50% epiphyte hydrophobic protein, 8%-40% glycols, 5%-30% silica-based surfactant.
Further, the water-based PVDF slurry of above-mentioned lithium ion battery, described glycols is enediol.
Further, the water-based PVDF slurry of above-mentioned lithium ion battery, described glycols is acetylenic glycols.
Further, the water-based PVDF slurry of above-mentioned lithium ion battery, the structural formula of described fluoro silica-based surfactant is as follows:
R is alkyl.
After of the present invention, a technical scheme is to provide the preparation method of the water-based PVDF slurry of described lithium ion battery, comprises the steps: successively
1) want to take each component at mass ratio described in 1 according to right;
2) by step 1) dispersant that takes is added in water, and stir 10 minutes, obtain mixed liquor A;
3) in mixed liquor A, step 1 is added) the PVDF powder stirring that takes 10 minutes, obtain mixed liquid B;
4) in mixed liquid B, step 1 is added) wetting agent that takes, to stir 30min.
Last technical scheme of the present invention, be to provide the using method of the water-based PVDF slurry of this lithium ion battery, the method comprises the steps: successively
1) in water-based PVDF slurry according to claim 1,1%-5% conductive agent is added, at normal temperatures to stir;
2) to step 1) in add active material and make its solid content at 90-96%, stir 120min; Add 0.05% ethylene glycol defoamer, can be applied on aluminium foil, then dry, make battery core.
Compared with prior art, technical scheme provided by the invention has following technological merit:
1, application of active dispersant of the present invention and wetting agent, containing hydrophobic and hydrophilic two property groups in special active dispersing agents, forms hydrophilic radical at PVDF particle surface, is convenient to PVDF well to disperse or dissolve in aqueous solvent.
2, the present invention is without CMC and SBR water-base cement, with some lower boiling surfactants, volatilizees, do not remain in positive pole in positive pole coating because of under high-temperature baking.Simultaneously, the dispersant added in the present invention and wetting agent to the conductive agent in positive pole as carbon nano-tube and Graphene have extraordinary dispersion effect, also good peptizaiton is had to active material such as the inorganic particle powders such as cobalt acid lithium, LiFePO4, ternary of positive pole, be convenient to be coated into uniform, stable anode pole piece, the cycle life of battery and high rate performance are improved a lot.
Accompanying drawing explanation
Fig. 1 is circulating battery curve chart prepared by water-based PVDF slurry provided by the invention;
Fig. 2 is battery different multiplying discharge performance prepared by water-based PVDF slurry provided by the invention.
Embodiment
Mode below by embodiment further illustrates the present invention, but does not form any limitation of the invention, and the amendment of anyone limited number of time made in right of the present invention is still in right of the present invention.
Embodiment 1
The water-based PVDF slurry of another kind of lithium ion battery provided by the invention, its solid content is 1%; In every 100g slurry, the mass percent of each component is, PVDF powder 20g, epiphyte hydrophobic protein HFBI10g, ethylene glycol bis (propionitrile) ether 0.2g, surplus is water.
Embodiment 2
The water-based PVDF slurry of another kind of lithium ion battery provided by the invention, its solid content is 7%; In every 100g slurry, the mass percent of each component is, PVDF powder 0.05g, epiphyte hydrophobic protein HFBII1g, ethylene glycol bis (propionitrile) ether 5g, surplus is water.
Embodiment 3
The water-based PVDF slurry of another kind of lithium ion battery provided by the invention, its solid content is 5%; In every 100g slurry, the mass percent of each component is, PVDF powder 10g, Isosorbide-5-Nitrae-butylene glycol 50g, ethylene glycol bis (propionitrile) ether 3g, surplus is water.
Embodiment 4
The water-based PVDF slurry of another kind of lithium ion battery provided by the invention, its solid content is 20%; In every 100g slurry, the mass percent of each component is, PVDF powder 12g, butynediols 0.1g, ethylene glycol bis (propionitrile) ether 1g, surplus is water.
Embodiment 5
The water-based PVDF slurry of another kind of lithium ion battery provided by the invention, its solid content is 12%; In every 100g slurry, the mass percent of each component is, PVDF powder 8g, epiphyte hydrophobic protein HFBI type 1g, butynediols 1g, ethylene glycol bis (propionitrile) ether 1g, surplus is water.
Embodiment 6
The water-based PVDF slurry of another kind of lithium ion battery provided by the invention, its solid content is 18%; In every 100g slurry, the mass percent of each component is, PVDF powder 16g, epiphyte hydrophobic protein HFBI type 1g, Isosorbide-5-Nitrae-butylene glycol 0.8g,
ethylene glycol bis (propionitrile) ether 3g, surplus is water.
Its preparation method is:
1) each component is taken by one group of mass number any in embodiment 1 to 6;
2) by step 1) dispersant that takes is added in water, and stir 10 minutes, obtain mixed liquor A;
3) in mixed liquor A, step 1 is added) the PVDF powder that takes, stirs 10 minutes, obtains mixed liquid B;
4) in mixed liquid B, step 1 is added) ethylene glycol bis (propionitrile) ether that takes, to stir 30min.
The using method of the water-based PVDF slurry of this lithium ion battery, comprises the steps: successively
1) add 1g-5g conductive agent by above-mentioned water-based PVDF slurry, at normal temperatures to stir 20min, after 5000r/min at a high speed under stir 30min;
2) to step 1) in add active material (material such as sour lithium, LiFePO4, ternary) and make its solid content under 90 to 96%, 3000r/min, stir 120min; Add 0.05g ethylene glycol defoamer, can be applied on aluminium foil, then dry, make battery core.
It should be noted that, water-based PVDF slurry provided by the invention, when practical application according to the conventional solid content requirement in this area, be diluted with water to solid content 1% to 3.5%, carrying out aforesaid operations.
Applying battery prepared by water-based PVDF slurry of the present invention, to make the high temperature storage data of battery as follows:
As can be seen from Table 1, the battery made with water-based PVDF slurry provided by the invention, 85 DEG C of full electricity store 4 hours thickness only to be increased less than 5%, and capacity restoration rate is to more than 95%.As can be seen from Figure 1 the capacity that 300 times also have 90% is recycled to, more high than 80% of current industry requirement.As can be seen from Figure 2,5C multiplying power releases the capacity of more than 90%, and these are enough to the battery that application water-based PVDF slurry provided by the invention is made, and bonding even, firm, interface stability, high-temperature behavior is good.
Can be found out by table 1, Fig. 1, Fig. 2, adopt battery prepared by water-based PVDF slurry provided by the invention, cycle performance, discharge performance are good.
Claims (10)
1. a water-based PVDF slurry for lithium ion battery, is characterized in that, calculates by gross mass 100%, and the mass percent of each component is, PVDF powder 0.05%-20%, dispersant 0.1%-10%, wetting agent 0.2%-5%, and surplus is water.
2. the water-based PVDF slurry of lithium ion battery according to claim 1, is characterized in that, the water-based PVDF slurry solid content of described lithium ion battery is 0.05-20%.
3. the water-based PVDF slurry of lithium ion battery according to claim 1, is characterized in that, described wetting agent is ethylene glycol bis (propionitrile) ether.
4. the water-based PVDF slurry of lithium ion battery according to claim 1, is characterized in that, described dispersant is one of them or combination in any of epiphyte hydrophobic protein or glycols or silica-based surfactant.
5. the water-based PVDF slurry of lithium ion battery according to claim 4, is characterized in that, described dispersant calculates by gross mass 100%, is made up of 10%-50% epiphyte hydrophobic protein, 8%-40% glycols, 5%-30% silica-based surfactant.
6. the water-based PVDF slurry of the lithium ion battery according to claim 4 or 5, is characterized in that, described glycols is enediol.
7. the water-based PVDF slurry of the lithium ion battery according to claim 4 or 5, is characterized in that, described glycols is acetylenic glycols.
8. the water-based PVDF slurry of lithium ion battery according to claim 4, is characterized in that, the structural formula of described fluoro silica-based surfactant is as follows:
R is alkyl.
9. prepare the water-based PVDF slurry of lithium ion battery according to claim 4, it is characterized in that, comprise the steps: successively
1) want to take each component at mass ratio described in 1 by right;
2) by step 1) dispersant that takes is added in water, and stir 8-12 minute, obtain mixed liquor A;
3) in mixed liquor A, step 1 is added) the PVDF powder stirring 8-12 minute that takes, obtain mixed liquid B;
4) in mixed liquid B, step 1 is added) wetting agent that takes, stir and evenly mix and get final product.
10. the using method of the water-based PVDF slurry of lithium ion battery according to claim 1, is characterized in that, comprise the steps: successively
1) in water-based PVDF slurry according to claim 1,1%-5% conductive agent is added, at normal temperatures to stir;
2) to step 1) in add active material and make its solid content at 90-96%, stir 120min; Add 0.05% ethylene glycol defoamer, can be applied on aluminium foil, then dry, make battery core.
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| CN201510452494.1A CN105119000B (en) | 2015-07-27 | 2015-07-27 | The aqueous PVDF slurries and its preparation, application method of a kind of lithium ion battery |
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| CN201510452494.1A CN105119000B (en) | 2015-07-27 | 2015-07-27 | The aqueous PVDF slurries and its preparation, application method of a kind of lithium ion battery |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100304270A1 (en) * | 2009-05-29 | 2010-12-02 | Arkema Inc. | Aqueous polyvinylidene fluoride composition |
| 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 |
-
2015
- 2015-07-27 CN CN201510452494.1A patent/CN105119000B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100304270A1 (en) * | 2009-05-29 | 2010-12-02 | Arkema Inc. | Aqueous polyvinylidene fluoride composition |
| 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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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