CN111883726A - Lithium ion battery diaphragm slurry and preparation method and application thereof - Google Patents
Lithium ion battery diaphragm slurry and preparation method and application thereof Download PDFInfo
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- 239000002002 slurry Substances 0.000 title claims abstract description 65
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000007613 slurry method Methods 0.000 title description 2
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 72
- 239000006185 dispersion Substances 0.000 claims description 65
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 28
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 28
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 28
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000004094 surface-active agent Substances 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 16
- 239000000839 emulsion Substances 0.000 claims description 16
- 239000002033 PVDF binder Substances 0.000 claims description 14
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 10
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- 238000005054 agglomeration Methods 0.000 claims description 3
- 230000002776 aggregation Effects 0.000 claims description 3
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 18
- 239000011248 coating agent Substances 0.000 abstract description 13
- 230000008569 process Effects 0.000 abstract description 13
- 238000002955 isolation Methods 0.000 abstract description 6
- 239000002245 particle Substances 0.000 abstract description 4
- 239000007888 film coating Substances 0.000 abstract description 3
- 238000009501 film coating Methods 0.000 abstract description 3
- 239000007921 spray Substances 0.000 abstract description 2
- 238000005507 spraying Methods 0.000 abstract description 2
- 238000012546 transfer Methods 0.000 abstract description 2
- 239000012528 membrane Substances 0.000 description 27
- 239000007787 solid Substances 0.000 description 15
- 230000000694 effects Effects 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 230000035699 permeability Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 230000005611 electricity Effects 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000003068 static effect Effects 0.000 description 5
- 230000004888 barrier function Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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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
-
- 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)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Cell Separators (AREA)
- Paints Or Removers (AREA)
Abstract
The invention provides lithium ion battery diaphragm slurry and a preparation method and application thereof, wherein the slurry comprises the following raw materials: compared with the prior art, the slurry prepared by the method does not need to be filtered, has no particles, has lower viscosity and better viscosity consistency, can be suitable for various isolation film coating processes, such as novel rotary spraying and traditional micro-concave roller transfer coating, and can prolong the service life of a rotary spray head and the micro-concave roller of the isolation film.
Description
Technical Field
The invention belongs to the field of battery materials, relates to a coating process of a lithium battery isolating membrane, and particularly relates to lithium ion battery diaphragm slurry as well as a preparation method and application thereof.
Background
In a lithium battery, an isolation film is one of the very critical components in the composition of the lithium battery, and the isolation film is mainly used for isolating a positive electrode and a negative electrode to prevent short circuit, and only allows lithium ions to shuttle between the positive electrode and the negative electrode, thereby playing a vital role in the internal resistance, the cycle performance, the internal resistance cycle of the lithium ion battery and the safety performance of the lithium ion battery.
The current industry membrane slurry generally needs to be filtered and is easy to precipitate, which is not beneficial to the control of the coating process.
Disclosure of Invention
The invention aims to provide lithium ion battery diaphragm slurry which improves the coating quality of a diaphragm.
The invention also aims to provide a preparation method of the lithium ion battery diaphragm slurry, the prepared lithium ion battery diaphragm slurry has better dispersion effect and better viscosity consistency, the coating and drying effect of the isolating membrane is improved, no crack appears after drying, and the method can be applied to various isolating membrane coating processes.
The last purpose of the invention is to provide application of the lithium ion battery diaphragm slurry to manufacturing of the lithium ion battery.
The specific technical scheme of the invention is as follows:
the lithium ion battery diaphragm slurry comprises the following raw materials in percentage by mass:
PVDF 7.86-8.70％
17.38 to 19.98 percent of aluminum oxide
Sodium carboxymethyl cellulose solution 11.13-12.41%
Ethylene carbonate 2.04-2.26%
Acrylic emulsion 3.79-4.19%
0.20 to 0.24 percent of surfactant
52.06-57.56% of deionized water;
the sum of the mass percentages of the raw materials is 100 percent.
The PVDF is polyvinylidene fluoride, is powder, is semitransparent or white and split in appearance, is tightly arranged in molecular chains, has strong hydrogen bonds, has an oxidation index of 45 percent, and is non-combustible. Particularly stable, the melting point is 172 ℃, and the long-term use temperature is-40-150 ℃.
The aluminum oxide is powder;
the surfactant is superwet 320.
The sodium carboxymethyl cellulose solution has a solid content of 1.3-1.8%.
The solid content of the acrylic emulsion is 45-55%.
The solid content of the obtained lithium ion battery diaphragm slurry is 28-32%.
The preparation method of the sodium carboxymethyl cellulose solution comprises the following steps: firstly, preparing deionized water and sodium carboxymethylcellulose required by solution preparation; then, 60-65% of the prepared deionized water is taken, sodium carboxymethylcellulose is added while stirring, after the addition is finished, the rest 35-40% of the deionized water is added, and is pre-stirred for 30-60min at the low speed of 800r/min under the condition of 40 +/-5 ℃, after no agglomeration, a high speed dispersion stirring stage of 1500 + 1800r/min is carried out, the temperature is 40 +/-5 ℃, and the stirring time is 400 + 500min, thus obtaining the sodium carboxymethylcellulose solution.
The invention provides a preparation method of lithium ion battery diaphragm slurry, which comprises the following steps:
1) adding PVDF powder and deionized water in a formula amount into a stirring tank, and performing low-speed dispersion stirring;
2) after stirring and dispersing uniformly, adding the aluminum oxide powder with the formula amount, and continuing to perform low-speed dispersion stirring;
3) then adding sodium carboxymethylcellulose solution with formula amount for low-speed dispersion and stirring;
4) then adding ethylene carbonate with the formula amount, and carrying out high-speed dispersion stirring;
5) adding the acrylic emulsion with the formula amount, and carrying out high-speed dispersion stirring;
6) finally, adding the surfactant with the formula amount, and carrying out high-speed dispersion stirring.
In the step 1), the low-speed dispersion stirring temperature is 40 +/-5 ℃, and the low-speed dispersion stirring speed is 600-;
in the step 2), the low-speed dispersion stirring temperature is 40 +/-5 ℃, and the low-speed dispersion stirring speed is 600 and the dispersion time is 800r/min and is 30-60 min.
In the step 3), the low-speed dispersion stirring temperature is 40 +/-5 ℃, the low-speed dispersion stirring speed is 600-800r/min, and the dispersion time is 60-120 min.
In the step 4), the high-speed dispersion stirring temperature is set to be 40 +/-5 ℃, the high-speed dispersion stirring speed is 1500-1800r/min, and the dispersion time is 90-150 min.
The high-speed dispersion stirring temperature in the step 5) is set to be 40 +/-5 ℃, the high-speed dispersion stirring speed is 1500-1800r/min, and the dispersion time is 30-60 min.
In the step 6), the high-speed dispersion stirring temperature is set to be 40 +/-5 ℃, the high-speed dispersion stirring speed is 1500-1800r/min, and the dispersion time is 30-60 min.
The method comprises the steps of preparing the isolating membrane slurry, testing the viscosity after shipment, selecting whether to adjust the viscosity according to the viscosity range, and putting the isolating membrane slurry into production for use after the viscosity is tested.
The application of the lithium ion battery diaphragm slurry prepared by the method is used for preparing the lithium ion battery.
The method comprises the step of adding PVDF and deionized water in the first step, wherein the PVDF is polyvinylidene fluoride, is semitransparent or white and split in appearance, is tightly arranged in molecular chains, has strong hydrogen bonds, has an oxidation index of 45 percent, and is non-combustible. The electrolyte is particularly stable, the melting point is 172 ℃, the long-term use temperature is-40-150 ℃, the oxidation resistance, the chemical corrosion resistance and the high-temperature resistance are excellent, the isolating membrane is arranged in the middle of the positive pole piece, heat is easily generated in the charging and discharging process, so that the isolating membrane using the chemical property temperature needs to be soaked in an acid electrolyte for a long time, and the PVDF is undoubtedly the best choice. Firstly, preliminarily dispersing PDVF, and then adding aluminium oxide powder, wherein the PVDF is added firstly because the aluminium oxide is insoluble in water, so that the aluminium oxide powder is uniformly dispersed in the PVDF solution, but both substances are easy to precipitate at the moment, and then adding a sodium carboxymethyl cellulose solution, wherein the sodium carboxymethyl cellulose has the advantages of thickening, stable dispersion and the like, and can effectively prevent precipitation. Then adding ethylene carbonate, wherein the ethylene carbonate is an organic solvent with excellent performance, and crystallization occurs at the room temperature of less than 35 ℃, so that high-speed dispersion is needed in the step, and the previous substances are dispersed more uniformly. And adding the acrylic emulsion after the step is finished, wherein the temperature of the battery isolating membrane can be generated in the charging and discharging processes, and the isolating membrane can be soaked in the electrolyte for a long time, so that the acrylic emulsion can improve the adhesive force of the slurry on one hand, and on the other hand, the acrylic emulsion also has excellent ageing resistance and acid and alkali resistance and has the function of removing static electricity in the coating process of the diaphragm. And finally, adding a surfactant which is superwet320, wherein bubbles are easily generated due to high-speed dispersion in the slurry manufacturing process, the surfactant can eliminate the bubbles on the surface of the slurry, and the coating of the slurry and the surface of the isolating membrane can be replaced, so that the isolating membrane is mainly soaked, the slurry is better coated, and the block-shaped missing coating generated by the coating of the isolating membrane due to the surface tension of water is reduced.
In the invention, the sodium carboxymethyl cellulose solution prevents slurry from precipitating, and has better dispersion effect and better viscosity consistency. The ethylene carbonate can improve the coating and drying effects of the isolating membrane, cracks can not appear after drying, and the shrinkage resistance effect is achieved in the drying process. In the isolating film coating process, the isolating film is mainly made of two materials of PP (polypropylene) and PE (polyethylene), internal static electricity is easily generated by transmission friction in the coating machine process, the acrylic emulsion can be uniformly dispersed into the isolating film slurry after being dispersed at a high speed, the static electricity cannot be generated after the acrylic emulsion is coated and dried, and the acrylic emulsion plays a role in removing the static electricity. The superwet320 surfactant can improve the surface tension of liquid, can better coat the isolating membrane slurry on an isolating membrane substrate, can remove bubbles on the surface of the isolating membrane slurry, and can improve the problem of coating blocky missing coating of the isolating membrane. In the preparation process, the temperature is set to be 40 +/-5 ℃, the relative motion activity among various material molecules can be kept, and a good dispersion effect can be achieved. If the surfactant is not added, bubbles are easily formed in the slurry in the stirring process and float on the surface of the slurry, the fine bubbles are transferred to the isolating membrane by the gravure roller, the isolating membrane enters the drying process of the oven, the bubbles are easily cracked to form circular ring-shaped missing coating, and the corresponding process flow cannot be achieved. If no sodium carboxymethyl cellulose is added or the addition amount is insufficient, the slurry is very easy to precipitate, so that the slurry is easy to form particles on the gravure roller, and the service life of the gravure roller is greatly shortened.
Compared with the prior art, the slurry prepared by the method disclosed by the invention is free of filtration, particles, lower in viscosity and better in viscosity consistency, and can be suitable for various isolation film coating processes, such as novel rotary spraying and traditional micro-concave roller transfer coating, and meanwhile, the service life of a rotary spray head can be prolonged, and the service life of an isolation film micro-concave roller can also be prolonged.
Drawings
FIG. 1 is a graph of the change in viscosity of the slurry prepared in example 1;
FIG. 2 is a graph of the viscosity change of the slurry produced in the present invention for half a month;
FIG. 3 is a comparison of the air permeability of the membranes prepared from the slurries of example 1 and comparative example 1, with sample number on the abscissa and air permeability on the ordinate, in sec/100cc units;
figure 4 is a comparison of the viscosity of the slurries of example 1 and comparative example 2, with the time measured on the abscissa and the product viscosity in mpa.s on the ordinate.
Detailed Description
Example 1
100 kilograms of lithium ion battery diaphragm slurry is fed with 30 percent of solid content, ethylene carbonate and a surfactant do not participate in the related calculation of the solid content in a formula research and development system, and the dosage of each raw material is as follows:
PVDF 8.28kg
18.83kg of aluminum oxide
11.72kg of sodium carboxymethylcellulose solution with a solid content of 1.6%
Ethylene carbonate 2.15kg
3.99kg of acrylic emulsion having a solids content of 50%
superwet320 surfactant 0.22kg
54.81kg deionized water.
The preparation method of the sodium carboxymethylcellulose solution with the solid content of 1.6 percent comprises the following steps: firstly, preparing deionized water and sodium carboxymethylcellulose required by solution preparation; and then, adding 65% of deionized water into sodium carboxymethylcellulose while stirring, adding the rest 35% of deionized water, pre-stirring for 30min at the low speed of 600r/min at the temperature of 40 +/-5 ℃, and performing a high-speed dispersion stirring stage at the speed of 1600r/min after no agglomeration, wherein the temperature is 40 +/-5 ℃, and the stirring time is 400min, thus obtaining the sodium carboxymethylcellulose solution.
The preparation method of the lithium ion battery diaphragm slurry comprises the following steps:
1) adding PVDF powder and deionized water in a formula amount into a stirring tank, and performing low-speed dispersion stirring: at the temperature of 40 +/-5 ℃, the low-speed dispersion stirring speed is 600r/min, and the dispersion stirring is carried out for 30 min;
2) after stirring and dispersing uniformly, adding the aluminum oxide powder with the formula amount, and continuing to perform low-speed dispersion stirring; at the temperature of 40 +/-5 ℃, the low-speed dispersion stirring speed is 600r/min, and the dispersion stirring is carried out for 30 min.
3) Then adding sodium carboxymethylcellulose solution with the formula amount for low-speed dispersion and stirring; at the temperature of 40 +/-5 ℃, the low-speed dispersion stirring speed is 600r/min, and the dispersion stirring is 60 min.
4) And adding ethylene carbonate according to the formula amount, and performing high-speed dispersion stirring at the high-speed dispersion stirring speed of 1700r/min and the dispersion stirring time of 90min at the temperature of 40 +/-5 ℃.
5) Adding the acrylic emulsion with the formula amount, and carrying out high-speed dispersion stirring; under the condition of 40 +/-5 ℃, the high-speed dispersion stirring speed is 1700r/min, and the dispersion stirring time is 30 min.
6) Finally, adding the surfactant with the formula amount, and carrying out high-speed dispersion stirring; under the condition of 40 plus or minus 5 ℃, the high-speed dispersion stirring speed is 1700r/min, and the dispersion stirring is 30 min.
7) And finally, testing the viscosity, and putting the isolating membrane slurry into production for use after the viscosity is tested.
The slurry prepared according to the method of example 1 was placed in a temperature and humidity environment (viscosity data measured in a low temperature and low humidity environment with a temperature of 16-24 ℃ and a humidity of less than 10%) satisfying the process requirements, and the viscosity data measured at different times were shown in fig. 1. The slurry prepared by the method of the embodiment 1 has very small viscosity change within 34H, almost has no change, and the bottom condition of the slurry has no precipitation, and is produced according to the general enterprises, even if one tank of slurry is consumed every day (24H), the slurry prepared by the method can well meet the requirement of corresponding process production due to very small viscosity change of the slurry within 24H.
Viscosity data measured for the slurries prepared according to the method of example 1, half a month per tank of barrier film slurry shipment are shown in figure 2. The direct viscosity consistency of slurry in each tank is better within half a month, and the direct difference between the tanks is very small, which indicates that the product has good stability and consistency.
The slurry prepared by the method has good consistency, no sediment is formed, the abrasion to the gravure roller is naturally minimized, and the abrasion to equipment is reduced to the minimum by using other processes, so that the service life of the gravure roller can be prolonged. The anti-shrinkage is the effect of ethylene carbonate, the ethylene carbonate is difficult to volatilize after the coated isolating membrane enters an oven (the oven temperature is generally 40-60 ℃) for drying because the boiling point of the ethylene carbonate is higher than 248 ℃, and cracks can not be caused by thorough drying in the drying process of the isolating membrane because the corresponding ethylene carbonate can be remained on the surface of the isolating membrane all the time. The ethylene carbonate remained on the surface of the isolating membrane does not influence the lithium battery, because the ethylene carbonate is also a very good electrolyte and can be finally integrated with the electrolyte in the lithium battery. The slurry has the function of removing static electricity into acrylic emulsion, the acrylic emulsion is mainly used as a binder, is non-toxic, harmless and environment-friendly, and is easy to dissolve in water and particularly well dispersed, so that the acrylic emulsion is particularly suitable as the binder of the isolating membrane slurry. The air bubble removal is a surfactant effect, is a product obtained by adding 9 ethylene oxide molecules to alkylphenol with alkyl carbon chain containing 8-12 carbon atoms, and has good wetting and penetration effects, the effect of inhibiting air bubbles on the surface of slurry and the like.
Comparative example 1
Compared with the method for preparing the lithium ion battery separator slurry in the example 1, the method is the same as the preparation method in the example 1 except that the superwet320 surfactant is not added.
The separators obtained using the slurries prepared in example 1 and comparative example 1 were subjected to a gas permeability test, which means the degree to which an object or medium allows gas to pass through, and a numerical value can be obtained by measuring the magnitude of the gas permeability per unit volume or section under a specific pressure and unit time.
Example 1 and comparative example 1 the experimental barrier film was 5 μm thick and the experimental data were data from one person using a coater before and after the same coater and the data were randomly sampled in sec/100cc for the coating process and the barrier film industry specific air permeability unit representing the time required for a 100cc volume of gas to permeate the barrier film with a process standard of 50-300(sec/100 cc). The results of the air permeability test of the separators obtained from the slurries prepared in example 1 and comparative example 1 are shown in fig. 3.
As can be seen from fig. 3, the air permeability of the release liner after the slurry without the surfactant is coated is out of the process range, and the air permeability is significantly better than that of the release liner with the surfactant, mainly because the surfactant is not added, the slurry is aqueous slurry, the main solvent is deionized water, and because the surface of water has liquid surface tension, when the slurry is coated on the release liner product, because of the surface tension of water, the slurry can shrink rapidly on the surface of the release liner, and cannot be well infiltrated, and because the surfactant does not exist, bubbles cannot be eliminated, and after the bubbles are coated on the surface of the release liner, the bubbles can also form a blocky coating leakage shape rapidly. The air permeability data will eventually be measured to be significantly better than a uniformly coated release film sample.
Comparative example 2
The preparation method of the lithium ion battery separator slurry is the same as that of example 1 except that a sodium carboxymethyl cellulose solution with a solid content of 0.8% is added.
The feeding was carried out according to the preparation method of example 1, the experimental data are all data taken by one person, the first tank material has 1.6% of sodium carboxymethyl cellulose solid content (another tank of slurry produced by the method of example 1), a sample is taken after stirring is finished, standing is carried out for measuring the viscosity, the second tank material is used for feeding by the same equipment after the first tank is finished, other materials are completely consistent, the sodium carboxymethyl cellulose solution is replaced by 0.8% of solid content solution (comparative example 2), then standing is carried out for measuring the viscosity, and the experimental data are shown in figure 4. (after the first tank is filled, the second tank is filled, the cleaning equipment is needed to remove the influence, and the filling of one tank takes 5 hours, and the viscosity data of the second tank is 6 hours later than that of the first tank by adding the cleaning and feeding time). (in this set of tests, the test set had 30% solids and the control had 29.9% solids, with little difference in solids, so the comparative test ignored the effect of solids on slurry viscosity.)
The 1.6% sodium carboxymethyl cellulose solution has very good temperature property and very stable viscosity corresponding to the pulp, while the 0.8% sodium carboxymethyl cellulose solution (comparative example 2) has very poor stability corresponding to the pulp, the viscosity is kept relatively stable within one hour, the precipitation is obviously generated after one hour, the viscosity is obviously reduced, and particles are easily formed after the precipitation, so that the service life of the gravure roller is greatly reduced.
Claims (10)
1. The lithium ion battery diaphragm slurry is characterized by comprising the following raw materials in parts by weight:
PVDF 7.86-8.70％
17.38 to 19.98 percent of aluminum oxide
Sodium carboxymethyl cellulose solution 11.13-12.41%
Ethylene carbonate 2.04-2.26%
Acrylic emulsion 3.79-4.19%
0.20 to 0.24 percent of surfactant
52.06-57.56% of deionized water;
the sum of the mass percentages of the raw materials is 100 percent.
2. The lithium ion battery separator slurry of claim 1, wherein the surfactant is superwet 320.
3. The lithium ion battery separator paste according to claim 1 or 2, wherein the preparation method of the sodium carboxymethyl cellulose solution comprises the following steps: firstly, preparing deionized water and sodium carboxymethylcellulose required by solution preparation; then, 60-65% of the prepared deionized water is taken, sodium carboxymethylcellulose is added while stirring, after the addition is finished, the rest 35-40% of the deionized water is added, and is pre-stirred for 30-60min at the low speed of 800r/min under the condition of 40 +/-5 ℃, after no agglomeration, a high speed dispersion stirring stage of 1500 + 1800r/min is carried out, the temperature is 40 +/-5 ℃, and the stirring time is 400 + 500min, thus obtaining the sodium carboxymethylcellulose solution.
4. A method for preparing the lithium ion battery separator slurry of any one of claims 1-3, comprising the steps of:
1) adding PVDF powder and deionized water in a formula amount into a stirring tank, and performing low-speed dispersion stirring;
2) after stirring and dispersing uniformly, adding the aluminum oxide powder with the formula amount, and continuing to perform low-speed dispersion stirring;
3) then adding sodium carboxymethylcellulose solution with formula amount for low-speed dispersion and stirring;
4) then adding ethylene carbonate with the formula amount, and carrying out high-speed dispersion stirring;
5) adding the acrylic emulsion with the formula amount, and carrying out high-speed dispersion stirring;
6) finally, adding the surfactant with the formula amount, and carrying out high-speed dispersion stirring.
5. The preparation method as claimed in claim 4, wherein the low-speed dispersion stirring temperature in step 1) is 40 ± 5 ℃, and the low-speed dispersion stirring speed is 600-800r/min for 30-60 min.
6. The preparation method as claimed in claim 4, wherein the low-speed dispersing and stirring temperature in step 2) is 40 ± 5 ℃, and the low-speed dispersing and stirring speed is 600-.
7. The preparation method as claimed in claim 4, wherein the low-speed dispersing and stirring temperature in step 3) is 40 ± 5 ℃, the low-speed dispersing and stirring speed is 600-800r/min, and the dispersing time is 60-120 min.
8. The method as claimed in claim 4, wherein the high speed dispersion stirring temperature in step 4) is set to 40 ± 5 ℃, the high speed dispersion stirring speed is 1500-.
9. The preparation method as claimed in claim 4, wherein the high speed dispersion stirring temperature in step 5) is set to 40 ± 5 ℃, the high speed dispersion stirring speed is 1500-;
in the step 6), the high-speed dispersion stirring temperature is set to be 40 +/-5 ℃, the high-speed dispersion stirring speed is 1500-1800r/min, and the dispersion time is 30-60 min.
10. Use of the lithium ion battery separator paste according to any of claims 1 to 3 for the preparation of a lithium ion battery.
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