CN114614201B - Zebra coated diaphragm and preparation method thereof - Google Patents
Zebra coated diaphragm and preparation method thereof Download PDFInfo
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- CN114614201B CN114614201B CN202210320763.9A CN202210320763A CN114614201B CN 114614201 B CN114614201 B CN 114614201B CN 202210320763 A CN202210320763 A CN 202210320763A CN 114614201 B CN114614201 B CN 114614201B
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- 241000283070 Equus zebra Species 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 238000000576 coating method Methods 0.000 claims abstract description 112
- 239000011248 coating agent Substances 0.000 claims abstract description 100
- 239000002002 slurry Substances 0.000 claims abstract description 49
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 20
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims abstract description 18
- CVJYOKLQNGVTIS-UHFFFAOYSA-K aluminum;lithium;titanium(4+);phosphate Chemical compound [Li+].[Al+3].[Ti+4].[O-]P([O-])([O-])=O CVJYOKLQNGVTIS-UHFFFAOYSA-K 0.000 claims abstract description 18
- 238000000605 extraction Methods 0.000 claims description 89
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 49
- 238000007774 anilox coating Methods 0.000 claims description 48
- 238000003756 stirring Methods 0.000 claims description 31
- 229920001328 Polyvinylidene chloride Polymers 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 28
- 239000005033 polyvinylidene chloride Substances 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 17
- -1 polyethylene Polymers 0.000 claims description 16
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 claims description 14
- 239000012528 membrane Substances 0.000 claims description 12
- 239000004698 Polyethylene Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 229920000573 polyethylene Polymers 0.000 claims description 11
- 238000013019 agitation Methods 0.000 claims 1
- 239000002033 PVDF binder Substances 0.000 abstract description 30
- 229920002981 polyvinylidene fluoride Polymers 0.000 abstract description 30
- 239000003795 chemical substances by application Substances 0.000 abstract description 20
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 15
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 15
- 230000014759 maintenance of location Effects 0.000 abstract description 7
- 150000002500 ions Chemical class 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 6
- 239000002245 particle Substances 0.000 abstract description 4
- 239000007791 liquid phase Substances 0.000 abstract description 2
- 239000012071 phase Substances 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 239000008367 deionised water Substances 0.000 description 40
- 229910021641 deionized water Inorganic materials 0.000 description 40
- 239000003792 electrolyte Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 17
- 238000012360 testing method Methods 0.000 description 17
- 239000007788 liquid Substances 0.000 description 13
- 239000006255 coating slurry Substances 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000004576 sand Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 230000009194 climbing Effects 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 229910000398 iron phosphate Inorganic materials 0.000 description 3
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical group [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000007755 gap coating Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
- H01M50/461—Separators, membranes or diaphragms characterised by their combination with electrodes with adhesive layers between electrodes and separators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/417—Polyolefins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Cell Separators (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
The invention discloses a zebra coated diaphragm and a preparation method thereof, wherein the related zebra coated diaphragm comprises the following components: the coating is parallel to each other and is arranged at intervals; the coating is coated with PVDF slurry. In the process of preparing PVDF slurry, high-ratio non-solvent cyclohexane and polyethylene glycol are adopted, wherein the cyclohexane is a gas-phase pore-forming agent, the polyethylene glycol is a liquid-phase pore-forming agent, and the high-content non-solvent ensures that the internal structure of a coating formed on a base film is filiform, so that a shuttle channel of lithium ions is enlarged, and the ion conductivity of a battery is improved. Meanwhile, lithium titanium aluminum phosphate particles are added in the wire-shaped coating, holes are left on the wire-shaped coating after lithium ions are released in the lithium titanium aluminum phosphate particles, so that a shuttle channel of the lithium ions is increased, the capacity retention rate of the battery can be improved, and the cycle life of the battery is prolonged.
Description
Technical Field
The invention belongs to the technical field of battery diaphragms, and particularly relates to a zebra coated diaphragm and a preparation method thereof.
Background
The safety coefficient of the power battery can be reduced along with the increase of energy density, the safety performance of the power battery mainly considers the bonding performance of the diaphragm and the pole piece, the current market is more enthusiastic to PVDF coating, and the bonding performance between the diaphragm and the pole piece and the safety of the battery can be improved to a great extent by PVDF. However, if a glue coating layer exists between the diaphragm and the pole piece, a part of lithium ions will be blocked to shuttle, and a zebra stripe coated lithium battery diaphragm exists in the market, so that the charge and discharge efficiency of the battery can be greatly improved, although the binding force and the charge and discharge efficiency are improved, an ideal charge and discharge state can not be achieved, the zebra stripe coated on the diaphragm can lead to nonuniform air permeability of the diaphragm, so that the 'selectivity' of lithium ions can appear when the lithium ions shuttle the surface of the diaphragm, most of lithium ions can pass through a channel which is easier to pass through, and although lithium ions also pass through when the PVDF coating is coated, the speed is slower.
Disclosure of Invention
In view of the deficiencies of the prior art, the present invention is directed to a zebra coated membrane.
Another object of the present invention is to provide a method of preparing the above zebra coated separator.
It is another object of the present invention to provide a method of preparing a PVDF slurry.
The aim of the invention is achieved by the following technical scheme.
A zebra coated separator comprising: the coating comprises a base film and a coating coated on one side of the base film, wherein the coating is stripes which are parallel to each other and are arranged at intervals, the interval distance between every two adjacent stripes is 1-1.2 mm, the width of each stripe is 4-4.5 mm, and the thickness of each stripe is 1-3 mu m;
The coating is formed by coating PVDF slurry;
a method of preparing the PVDF slurry, comprising the steps of:
step 1, uniformly mixing lithium aluminum titanium phosphate and dimethylacetamide, and sanding to obtain slurry, wherein the ratio of the lithium aluminum titanium phosphate to the dimethylacetamide is (25-35) in parts by weight: (65-75);
In the step 1, the stirring speed of the uniform mixing is 30-40 r/min, and the stirring time is 30-50 min.
In the step 1, the sanding time is 15-30 min, and the sanding rotating speed is 500-800 r/min.
Step2, mixing the slurry obtained in the step 1 with polyvinylidene chloride until the polyvinylidene chloride is completely dissolved, adding cyclohexane, uniformly mixing, adding polyethylene glycol, and uniformly stirring to obtain PVDF slurry, wherein the ratio of the slurry to the polyvinylidene chloride to the cyclohexane to the polyethylene glycol is (30-36) in parts by weight: (4-10): (30-35): (25-30).
In the step 2, the stirring speed of the mixing is 30-40 r/min, and the stirring time is 30-50 min.
In the step 2, the stirring speed of the uniform mixing is 30-40 r/min, and the stirring time is 20-30 min.
In the step 2, the stirring speed of the uniform stirring is 30-40 r/min, and the stirring time is 20-30 min.
PVDF slurry obtained by the preparation method.
A method of preparing a zebra coated membrane comprising the steps of:
Step a, coating: coating PVDF slurry on one side of a base film by using an anilox roller, and forming a coating on the base film to obtain a diaphragm;
in the step a, strip-shaped bulges are arranged on the surface of the anilox roller and are used for forming a coating.
In the step a, the tangent line of the anilox roller and the base film is a tangent line, and the relative movement speed of the tangent line and the base film is 10-25 m/min.
In the step a, the base film is a polyethylene-based film.
Step b, extraction: and c, sequentially passing the diaphragm in the step a through 10-15 extraction tanks, and drying to obtain the zebra coating diaphragm, wherein the extractant in the 1 st-3 extraction tanks is a mixture of dimethylacetamide and water, and the extractant in the rest extraction tanks is water.
In the step b, the ratio of the dimethylacetamide to the water in the 1 st extraction tank is 3 in parts by weight: (1-2) the ratio of dimethylacetamide to water in the 2 nd extraction tank is 3: (3-4), the ratio of dimethylacetamide to water in the 3 rd extraction tank is 3: (4-6).
In the step b, the drying temperature is 50-70 ℃, and the drying time is 30-40 s.
In the step b, the extraction is performed at normal temperature.
In said step b, the extraction time in each extraction tank is 5-10 s.
In the process of preparing PVDF slurry, high-proportion non-solvent (namely cyclohexane and polyethylene glycol) is adopted, wherein the cyclohexane is a gas-phase pore-forming agent, and the polyethylene glycol is a liquid-phase pore-forming agent), and the high-content non-solvent enables the internal structure of a coating formed on a base film to be filiform, so that a shuttle channel of lithium ions is enlarged, and the ion conductivity of a battery is improved. Meanwhile, lithium titanium aluminum phosphate particles are added in the wire-shaped coating, holes are left on the wire-shaped coating after lithium ions are released in the lithium titanium aluminum phosphate particles, so that a shuttle channel of the lithium ions is increased, the capacity retention rate of the battery can be improved, and the cycle life of the battery is prolonged.
Drawings
FIG. 1 is a schematic illustration of the coating method of example 1 of the present invention;
FIG. 2 is an electron micrograph of the surface of a zebra coated membrane prepared in example 1 of the present invention.
Detailed Description
The technical scheme of the invention is further described below with reference to specific embodiments.
The relevant instruments and equipment used in the specific embodiment of the invention are as follows:
Rod pin type sand mill: NT-V30, dongguan, langmuir mechanical Co., ltd.
The related medicines used in the specific embodiment of the invention are as follows:
The polyethylene film thicknesses used in the examples and comparative examples of the present invention were 12 μm and the lengths were 1000mm.
The electrolyte of the electrolyte used in the tests of the following examples and comparative examples was lithium hexafluorophosphate, the solvent of the electrolyte was carbonate, and the concentration of the electrolyte in the electrolyte was 6mol/L.
Positive pole piece:
Drying iron phosphate at 540 ℃ for 5 hours to remove water, mixing the iron phosphate with lithium carbonate, filling the mixture into a die, pressing the die with 150 tons of hydraulic pressure for 10 minutes to form blocks, pushing the blocks into a push plate furnace, heating the push plate furnace to 500 ℃ for 5 hours, heating the push plate furnace to 750 ℃ for 8 hours, cooling the push plate furnace for 7 hours, grinding the push plate furnace into fine powder, and uniformly mixing the fine powder, N-methylpyrrolidone, PVP and PVDF to obtain the coating, wherein the ratio of the iron phosphate to the lithium carbonate is 5 in parts by weight: 1, the ratio of fines, N-methylpyrrolidone, PVP and PVDF is 40:55:2:3, a step of;
And (3) extruding and coating the coating on an aluminum plastic sheet, and drying at 105 ℃ for 4 hours to obtain the positive electrode sheet, wherein the coating amount is 45 g/square meter.
Negative pole piece:
Drying graphite powder at 200 ℃ for 5 hours to remove water, and mixing the graphite powder, N-methylpyrrolidone, PVP and PVDF to obtain the coating, wherein the ratio of the graphite powder to the N-methylpyrrolidone to the PVP to the PVDF is 45 in parts by weight: 50:2:3,
And (3) extruding and coating the coating on copper foil, and baking for 4 hours at 105 ℃ to obtain the negative electrode plate, wherein the coating amount is 32 g/square meter.
Example 1
A zebra coated separator comprising: the base film and the coating coated on one side of the base film, wherein the coating is parallel to each other and is provided with strips at intervals, the interval distance between adjacent strips is 1mm, the width of each strip is 4mm, and the thickness of each strip is 1 mu m.
The coating is formed by coating PVDF slurry;
A method of preparing a PVDF slurry, comprising the steps of:
step 1, stirring lithium aluminum titanium phosphate and dimethylacetamide at 30r/min for 30min, uniformly mixing, and sanding with a rod pin type sand mill at 500r/min for 15min to obtain slurry, wherein the ratio of the lithium aluminum titanium phosphate to the dimethylacetamide is 35: 65.
Step 2, mixing the slurry obtained in the step 1 with polyvinylidene chloride at 30r/min until the polyvinylidene chloride is completely dissolved, adding cyclohexane, stirring for 20min at 30r/min, uniformly mixing, adding polyethylene glycol, stirring for 20min at 30r/min, and uniformly obtaining PVDF slurry, wherein the ratio of the slurry to the polyvinylidene chloride to the cyclohexane to the polyethylene glycol is 36 in parts by weight: 4:30:30.
The preparation method of the zebra coated diaphragm comprises the following steps:
Step a, coating: coating PVDF slurry on one side of a polyethylene-based film by using an anilox roller, and forming a coating on the base film to obtain a diaphragm, wherein strip-shaped bulges are arranged on the surface of the anilox roller and are used for forming the coating; the tangential line of the anilox roller and the base film is a tangential line, the relative movement speed of the tangential line and the base film is 10m/min, and in the coating process, the movement direction of the base film is the same as the rotation linear speed direction of the anilox roller, as shown in figure 1, the base film moves upwards, and the anilox roller rotates clockwise;
Step b, extraction: sequentially extracting the diaphragm in the step a through 10 extraction tanks with the depth of 1m, and drying at 50 ℃ for 30s to obtain a zebra coating diaphragm, wherein the extracting agent in the 1 st to 3 extraction tanks is a mixture of dimethylacetamide and deionized water, the extracting agent in the rest extraction tanks is deionized water, and the ratio of dimethylacetamide to deionized water in the 1 st extraction tank is 3:1, the ratio of dimethylacetamide to deionized water in the 2 nd extraction tank is 1:1, the ratio of dimethylacetamide to deionized water in the 3 rd extraction tank is 3:5, the extraction time in each extraction tank is 5s, and the temperature of the extractant is 20-25 ℃ at normal temperature.
In the coating process, the linear speed direction of the rotation of the anilox roller is consistent with the running direction of the base film, so that the linear speed of the anilox roller is consistent with the running speed of the base film, and the structure of the surface of the base film cannot be damaged in the coating process. The coating can enable the slurry to be adsorbed on the surface of the base film regularly, so that the boundary between the stripe of the coating and the stripe of the base film which is not coated is separated clearly, and the internal resistance of the battery is reduced.
As shown in fig. 2, the surface of the zebra coating diaphragm is of a three-dimensional wire-shaped structure, the aperture is uniform, lithium ions can easily shuttle between the apertures, and the adhesion of the zebra coating diaphragm and a lithium battery pole piece is facilitated.
Example 2
A zebra coated separator comprising: the base film and the coating coated on one side of the base film, wherein the coating is parallel to each other and is provided with strips at intervals, the interval distance between every two adjacent strips is 1.1mm, the width of each strip is 4.3mm, and the thickness of each strip is 2 mu m.
The coating is formed by coating PVDF slurry;
A method of preparing a PVDF slurry, comprising the steps of:
Step 1, stirring and uniformly mixing lithium aluminum titanium phosphate and dimethylacetamide at 35r/min for 35min, and sanding with a rod pin type sand mill at 500r/min for 20min to obtain slurry, wherein the ratio of the lithium aluminum titanium phosphate to the dimethylacetamide is 30 in parts by weight: 70;
Step 2, mixing the slurry obtained in the step 1 with polyvinylidene chloride at 35r/min for 40min until the polyvinylidene chloride is completely dissolved, adding cyclohexane, stirring for 25min at 35r/min, uniformly mixing, adding polyethylene glycol, stirring for 25min at 35r/min, and uniformly obtaining PVDF slurry, wherein the ratio of the slurry to the polyvinylidene chloride to the cyclohexane to the polyethylene glycol is 33:6:33:28.
The preparation method of the zebra coated diaphragm comprises the following steps:
Step a, coating: coating PVDF slurry on one side of a polyethylene-based film by using an anilox roller, and forming a coating on the base film to obtain a diaphragm, wherein strip-shaped bulges are arranged on the surface of the anilox roller and are used for forming the coating; the tangential line of the anilox roller and the base film is a tangential line, the relative movement speed of the tangential line and the base film is 18m/min, and in the coating process, the movement direction of the base film is the same as the rotation linear speed direction of the anilox roller, as shown in figure 1, the base film moves upwards, and the anilox roller rotates clockwise;
Step b, extraction: sequentially extracting the diaphragm in the step a through 13 extraction tanks with the depth of 1m, and drying at 60 ℃ for 35s to obtain a zebra coating diaphragm, wherein the extracting agent in the 1 st to 3 extraction tanks is a mixture of dimethylacetamide and deionized water, the extracting agent in the rest extraction tanks is deionized water, and the ratio of dimethylacetamide to deionized water in the 1 st extraction tank is 3:2, the ratio of dimethylacetamide to deionized water in the 2 nd extraction tank is 3:4, the ratio of dimethylacetamide to deionized water in the 3 rd extraction tank is 3:6, the extraction time in each extraction tank is 7s, and the temperature of the extractant is 20-25 ℃ at normal temperature.
Example 3
A zebra coated separator comprising: the base film and the coating coated on one side of the base film are parallel and spaced stripes, the spacing distance between adjacent stripes is 1.2mmnm, the width of each stripe is 4.5mm, and the thickness of each stripe is 3 mu m.
The coating is formed by coating PVDF slurry;
A method of preparing a PVDF slurry, comprising the steps of:
Step 1, stirring and uniformly mixing lithium aluminum titanium phosphate and dimethylacetamide at 40r/min for 40min, and sanding with a rod pin type sand mill at 500r/min for 30min to obtain slurry, wherein the ratio of the lithium aluminum titanium phosphate to the dimethylacetamide is 25 in parts by weight: 75;
Step 2, mixing the slurry obtained in the step 1 with polyvinylidene chloride at 40r/min for 50min until the polyvinylidene chloride is completely dissolved, adding cyclohexane, stirring for 30min at 40r/min, uniformly mixing, adding polyethylene glycol, stirring for 30min at 40r/min, and uniformly obtaining PVDF slurry, wherein the ratio of the slurry to the polyvinylidene chloride to the cyclohexane to the polyethylene glycol is 30 in parts by weight: 10:35:25.
The preparation method of the zebra coated diaphragm comprises the following steps:
step a, coating: coating PVDF slurry on one side of a polyethylene-based film by using an anilox roller, and forming a coating on the base film to obtain a diaphragm, wherein strip-shaped bulges are arranged on the surface of the anilox roller and are used for forming the coating; the tangential line of the anilox roller and the base film is a tangential line, the relative movement speed of the tangential line and the base film is 25m/min, and in the coating process, the movement direction of the base film is the same as the rotation linear speed direction of the anilox roller, as shown in figure 1, the base film moves upwards, and the anilox roller rotates clockwise;
step b, extraction: sequentially extracting the diaphragm in the step a through 15 extraction tanks with the depth of 1m, and drying the diaphragm at 70 ℃ for 40s to obtain a zebra coating diaphragm, wherein the extracting agent in the 1 st to 3 rd extraction tanks is a mixture of dimethylacetamide and deionized water, the extracting agent in the rest extraction tanks is deionized water, and the ratio of dimethylacetamide to deionized water in the 1 st extraction tank is 3:2, the ratio of dimethylacetamide to deionized water in the 2 nd extraction tank is 1:1, the ratio of dimethylacetamide to deionized water in the 3 rd extraction tank is 2:3, extracting time in each extraction tank is 10s, and the temperature of the extractant is 20-25 ℃ at normal temperature.
Comparative example 1
A coated separator comprising: the base film and the coating coated on one side of the base film, wherein the coating is parallel to each other and is provided with strips at intervals, the interval distance between every two adjacent strips is 1.2mm, the width of each strip is 4.5mm, and the thickness of each strip is 3 mu m.
The coating is formed by coating slurry;
A method of preparing a coating slurry comprising the steps of:
Mixing dimethylacetamide and polyvinylidene chloride at 35r/min for 30min until polyvinylidene chloride is completely dissolved, adding cyclohexane at 35r/min for stirring for 20min, adding polyethylene glycol at 35r/min for stirring for 20min, and obtaining coating slurry, wherein the ratio of dimethylacetamide to polyvinylidene chloride to cyclohexane to polyethylene glycol is 36 in parts by weight: 4:30:30.
The preparation method of the coated diaphragm comprises the following steps:
Step a, coating: coating the coating slurry on one side of a polyethylene-based film by using an anilox roller to form a coating on the base film to obtain a diaphragm, wherein strip-shaped bulges are arranged on the surface of the anilox roller and are used for forming the coating; the tangential line of the anilox roller and the base film is a tangential line, the relative movement speed of the tangential line and the base film is 10m/min, and in the coating process, the movement direction of the base film is the same as the rotation linear speed direction of the anilox roller, as shown in figure 1, the base film moves upwards, and the anilox roller rotates clockwise;
Step b, extraction: sequentially extracting the diaphragm in the step a through 10 extraction tanks with the depth of 1m, and drying at 50 ℃ for 30s to obtain a coated diaphragm, wherein the extracting agent in the 1 st to 3 rd extraction tanks is a mixture of dimethylacetamide and deionized water, the extracting agent in the rest extraction tanks is deionized water, and the ratio of dimethylacetamide to deionized water in the 1 st extraction tank is 3:2, the ratio of dimethylacetamide to deionized water in the 2 nd extraction tank is 1:1, the ratio of dimethylacetamide to deionized water in the 3 rd extraction tank is 2:3, the extraction time in each extraction tank is 5s, and the temperature of the extractant is 20-25 ℃ at normal temperature.
Comparative example 2
A coated separator comprising: the base film and the coating coated on one side of the base film, wherein the coating is parallel to each other and is provided with strips at intervals, the interval distance between every two adjacent strips is 1.2mm, the width of each strip is 4.5mm, and the thickness of each strip is 3 mu m.
The coating is formed by coating slurry;
A method of preparing a coating slurry comprising the steps of:
Step 1, stirring lithium aluminum titanium phosphate and dimethylacetamide at 35r/min for 30min, uniformly mixing, and sanding with a rod pin type sand mill at 500r/min for 15min to obtain slurry, wherein the ratio of the lithium aluminum titanium phosphate to the dimethylacetamide is 35: 65.
Step 2, mixing the slurry obtained in the step 1 with polyvinylidene chloride at the speed of 35r/min for 30min until the polyvinylidene chloride is completely dissolved, adding polyethylene glycol, stirring for 20min at the speed of 35r/min uniformly to obtain coating slurry, wherein the ratio of the slurry to the polyvinylidene chloride to the polyethylene glycol is 36 in parts by weight: 4:30.
The preparation method of the coated diaphragm comprises the following steps:
Step a, coating: coating the coating slurry on one side of a polyethylene-based film by using an anilox roller to form a coating on the base film to obtain a diaphragm, wherein strip-shaped bulges are arranged on the surface of the anilox roller and are used for forming the coating; the tangential line of the anilox roller and the base film is a tangential line, the relative movement speed of the tangential line and the base film is 10m/min, and in the coating process, the movement direction of the base film is the same as the rotation linear speed direction of the anilox roller, as shown in figure 1, the base film moves upwards, and the anilox roller rotates clockwise;
Step b, extraction: sequentially extracting the diaphragm in the step a through 10 extraction tanks with the depth of 1m, and drying at 50 ℃ for 30s to obtain a coated diaphragm, wherein the extracting agent in the 1 st to 3 rd extraction tanks is a mixture of dimethylacetamide and deionized water, the extracting agent in the rest extraction tanks is deionized water, and the ratio of dimethylacetamide to deionized water in the 1 st extraction tank is 3:2, the ratio of dimethylacetamide to deionized water in the 2 nd extraction tank is 1:1, the ratio of dimethylacetamide to deionized water in the 3 rd extraction tank is 2:3, extracting time in each extraction tank is 30s, and the temperature of the extractant is 20-25 ℃ at normal temperature.
Comparative example 3
A coated separator comprising: the base film and the coating coated on one side of the base film are parallel and spaced stripes, the spacing distance between adjacent stripes is 1.2mm, the width of each stripe is 4.5mm, and the thickness of each stripe is 3 mu m.
The coating is formed by coating slurry;
The time taken is 5s, and the temperature of the extractant is 20-25 ℃ at normal temperature.
A method of preparing a coating slurry comprising the steps of:
Step 1, stirring lithium aluminum titanium phosphate and dimethylacetamide at 35r/min for 30min, uniformly mixing, and sanding with a rod pin type sand mill at 500r/min for 15min to obtain slurry, wherein the ratio of the lithium aluminum titanium phosphate to the dimethylacetamide is 35: 65.
Step 2, mixing the slurry obtained in the step 1 with polyvinylidene chloride at the speed of 35r/min for 30min until the polyvinylidene chloride is completely dissolved, adding cyclohexane, stirring for 20min at the speed of 35r/min, uniformly mixing, adding polyethylene glycol, stirring for 20min at the speed of 35r/min, and uniformly obtaining coating slurry, wherein the ratio of the slurry to the polyvinylidene chloride to the cyclohexane to the polyethylene glycol is 13:4:20:10.
The preparation method of the coated diaphragm comprises the following steps:
Step a, coating: coating the coating slurry on one side of a polyethylene-based film by using an anilox roller to form a coating on the base film to obtain a diaphragm, wherein strip-shaped bulges are arranged on the surface of the anilox roller and are used for forming the coating; the tangential line of the anilox roller and the base film is a tangential line, the relative movement speed of the tangential line and the base film is 10m/min, and in the coating process, the movement direction of the base film is the same as the rotation linear speed direction of the anilox roller, as shown in figure 1, the base film moves upwards, and the anilox roller rotates clockwise;
Step b, extraction: sequentially extracting the diaphragm in the step a through 10 extraction tanks with the depth of 1m, and drying at 50 ℃ for 30s to obtain a coated diaphragm, wherein the extracting agent in the 1 st to 3 rd extraction tanks is a mixture of dimethylacetamide and deionized water, the extracting agent in the rest extraction tanks is deionized water, and the ratio of dimethylacetamide to deionized water in the 1 st extraction tank is 3:2, the ratio of dimethylacetamide to deionized water in the 2 nd extraction tank is 1:1, the ratio of dimethylacetamide to deionized water in the 3 rd extraction tank is 2:3 extraction in each extraction tank
Comparative example 4
A method of making a coated separator comprising the steps of:
Step a, coating: coating PVDF slurry prepared in the embodiment 1 on one side of a polyethylene-based film by using an anilox roller to form a coating on a base film to obtain a diaphragm, wherein lines with the depth of 2 mu m are uniformly distributed on the surface of the anilox roller, the axial angle of the lines and the anilox roller is 45 degrees, and the interval between adjacent lines is 0.5mm, so as to form a fully coated coating; in the coating process, the moving direction of the base film is opposite to the rotating linear speed direction of the anilox roller, the base film moves upwards, and the anilox roller rotates downwards anticlockwise;
Step b, extraction: sequentially extracting the diaphragm in the step a through 10 extraction tanks with the depth of 1m, and drying the diaphragm at 50 ℃ for 30s to obtain a zebra coating diaphragm, wherein the extraction temperature is 20-25 ℃, the extracting agent in the 1 st to 3 rd extraction tanks is a mixture of dimethylacetamide and deionized water, the extracting agent in the rest extraction tanks is deionized water, and the ratio of dimethylacetamide to deionized water in the 1 st extraction tank is 3:1, the ratio of dimethylacetamide to deionized water in the 2 nd extraction tank is 1:1, the ratio of dimethylacetamide to deionized water in the 3 rd extraction tank is 3:5, the extraction time in each extraction tank was 5s.
Comparative example 5
A coated separator comprising: the base film and the coating coated on one side of the base film are parallel and spaced stripes, the spacing distance between every two adjacent stripes is 10mm, the width of each stripe is 10mm, and the thickness of each stripe is 1 mu m.
The preparation method of the coated diaphragm comprises the following steps:
step a, coating: coating the PVDF slurry prepared in the example 1 on one side of a polyethylene-based film by using an anilox roller to form a coating on the base film to obtain a diaphragm, wherein the surface of the anilox roller is provided with strip-shaped bulges for forming a coated coating; the tangential line of the anilox roller and the base film is a tangential line, the relative movement speed of the tangential line and the base film is 10m/min, and in the coating process, the movement direction of the base film is the same as the rotation linear speed direction of the anilox roller, as shown in figure 1, the base film moves upwards, and the anilox roller rotates clockwise;
Step b, extraction: sequentially extracting the diaphragm in the step a through 10 extraction tanks with the depth of 1m, and drying the diaphragm at 50 ℃ for 30s to obtain a coated diaphragm, wherein the extraction temperature is 20-25 ℃, the extracting agent in the 1 st to 3 rd extraction tanks is a mixture of dimethylacetamide and deionized water, the extracting agent in the rest extraction tanks is deionized water, and the ratio of dimethylacetamide to deionized water in the 1 st extraction tank is 3 in parts by mass: 1, the ratio of dimethylacetamide to deionized water in the 2 nd extraction tank is 1:1, the ratio of dimethylacetamide to deionized water in the 3 rd extraction tank is 3:5, the extraction time in each extraction tank was 5s.
The adhesive force between the sample and the battery pole piece was tested, the sample was one of the zebra coated diaphragms obtained in examples 1 to 3 and the coated diaphragms obtained in comparative examples 1 to 5, and the adhesive force test method was: cutting the battery pole piece and the sample into rectangles of 12 multiplied by 100mm respectively, overlapping the two, and compacting the overlapped battery pole piece and the sample by using a battery pole piece press machine to prepare a test sample, wherein the pressure is 0.8Mpa, the temperature is 70 ℃ and the time is 20s; and tearing the battery pole piece of the test sample and the sample by using a pulling machine to obtain the binding force between the sample and the battery pole piece, wherein the positive electrode material of the battery is lithium iron phosphate, and the negative electrode material of the battery is graphite. The results are shown in Table 1.
TABLE 1
As can be seen from Table 1, the zebra coated separators prepared in examples 1 to 3 have smaller air permeability and stronger adhesion with the battery pole pieces, thereby improving the stability of the zebra coated separator and the safety performance of the battery.
The zebra coated separators obtained in examples 1 to 3 and the coated separators obtained in comparative examples 1 to 5 were subjected to ion conductivity test, and the test results are shown in table 2.
TABLE 2
Impedance is one of the important indicators for testing ion conductivity, the smaller the impedance, the higher the ion conductivity, the important indicator for detecting the number of lithium ion shuttle battery diaphragms, and the higher the ion conductivity is when the number of lithium ions penetrating through the battery diaphragms in unit time is. As can be seen from table 2, compared with comparative examples 1 to 5, the zebra coated separators prepared in examples 1 to 3 have higher ionic conductivity due to gap coating, which proves that the zebra coated separators prepared in examples greatly reduce the "selectivity" of lithium ions in the shuttle zebra coated separator.
The zebra coated diaphragms obtained in examples 1 to 3 and the coated diaphragms obtained in comparative examples 1 to 3 were subjected to tests of liquid absorption and retention, and the test results are shown in table 3.
The liquid absorption rate testing method comprises the following steps: the zebra coated diaphragms prepared in examples 1 to 3 and the coated diaphragms prepared in comparative examples 1 to 3 were cut to have a width of 30mm and a length of 100mm, weighed and recorded as a mass before soaking, soaked in an electrolyte (lithium hexafluorophosphate) for 30 minutes, taken out, weighed and recorded as a mass after soaking, and the liquid absorption (liquid absorption= (mass after soaking-mass before soaking)/mass before soaking) was calculated.
The liquid retention rate testing method comprises the following steps: the zebra coated diaphragms prepared in examples 1 to 3 and the coated diaphragms prepared in comparative examples 1 to 3 were immersed in an electrolyte (lithium hexafluorophosphate) for 30min, taken out and suspended for 30min, then the superfluous electrolyte on the surface was gently sucked up with a nonwoven fabric, weighed and recorded as the mass of the liquid-retaining diaphragm, and the liquid-retaining rate (liquid-retaining rate= (mass of liquid-retaining diaphragm-mass before immersion)/mass before immersion) was calculated.
TABLE 3 Table 3
As shown in table3, the liquid absorption and the liquid retention of the zebra coated membrane are both significantly improved, because the zebra coated membrane has a wire-shaped coating and uniform pore diameter, the liquid absorption and the liquid retention of the zebra coated membrane can be significantly improved.
The zebra coated separators obtained in examples 1 to 3 and the coated separators obtained in comparative examples 1 to 5 were subjected to an electrolyte wettability test, and the test results are shown in table 4.
Electrolyte (lithium hexafluorophosphate) wettability test method: cutting a sample into a rectangle with the length of 7 multiplied by 20mm, hanging the rectangle on the wall of a beaker, adding electrolyte into the beaker, immersing the electrolyte liquid level into the position with the length of 5mm at the tail end of the sample, marking the position as an initial height, recording time, checking the climbing height of the electrolyte on the sample, and testing the climbing height at different intervals.
TABLE 4 Table 4
As shown in table 4, compared with the comparative example, the liquid climbing height of the zebra coated membrane is higher with the increase of time, which indicates that the zebra coated membrane prepared in the example has good wettability, and the liquid climbing height is not only a key index for testing the liquid filling efficiency of the battery membrane during battery loading, but also an important index for testing the charge and discharge efficiency of the battery, so that it is particularly important to improve the electrolyte wettability of the battery membrane. The zebra coated diaphragm prepared by the embodiment adopts a filiform coating, the wettability of the zebra coated diaphragm can be greatly improved by adopting the structure, and the electrolyte can be gradually immersed into the whole battery along the grain by adopting the coating method of the invention.
The zebra coated separator obtained in examples 1 to 3 and the coated separator obtained in comparative examples 1 to 3 were wound into batteries (battery model number: NCM 606090) each having a thickness of 6mm, a width of 60mm, a length of 90mm, a nominal capacity of 4000mAh, an internal resistance of less than 40mΩ, and a nominal voltage of 3.7V, respectively.
The positive electrode material of the battery is lithium iron phosphate, the negative electrode material of the battery is graphite, the electrolyte of the electrolyte is lithium hexafluorophosphate, the solvent is carbonic ester, and the concentration of the electrolyte in the electrolyte is 6mol/L.
The assembled battery was subjected to capacity and rate cycling test, and the test results are shown in table 5.
TABLE 5
As can be seen from table 5, the battery prepared from the zebra coated separator prepared in the examples showed a slower rate of change in battery capacity after charging or discharging from low to high rate, compared with the comparative examples; after 50 cycles, the capacity retention of the cell was higher, and thus the life of the cell prepared with the zebra coated separator was longer.
The foregoing has described exemplary embodiments of the invention, it being understood that any simple variations, modifications, or other equivalent arrangements which would not unduly obscure the invention may be made by those skilled in the art without departing from the spirit of the invention.
Claims (9)
1. A zebra coated membrane comprising: the coating comprises a base film and a coating coated on one side of the base film, wherein the coating is stripes which are parallel to each other and are arranged at intervals, the interval distance between every two adjacent stripes is 1-1.2 mm, the width of each stripe is 4-4.5 mm, and the thickness of each stripe is 1-3 mu m;
The coating is formed by coating PVDC slurry;
A method of preparing the PVDC slurry comprising the steps of:
step 1, uniformly mixing lithium aluminum titanium phosphate and dimethylacetamide, and sanding to obtain slurry, wherein the ratio of the lithium aluminum titanium phosphate to the dimethylacetamide is (25-35) in parts by weight: (65-75);
Step2, mixing the slurry obtained in the step 1 with polyvinylidene chloride until the polyvinylidene chloride is completely dissolved, adding cyclohexane, uniformly mixing, adding polyethylene glycol, and uniformly stirring to obtain PVDC slurry, wherein the ratio of the slurry to the polyvinylidene chloride to the cyclohexane to the polyethylene glycol is (30-36) in parts by weight: (4-10): (30-35): (25-30).
2. The zebra coated membrane of claim 1, wherein in step 1, the stirring speed of the uniform mixing is 30-40 r/min, the stirring time is 30-50 min,
In the step 1, the sanding time is 15-30 min, and the sanding rotating speed is 500-800 r/min.
3. The zebra coated separator of claim 2, wherein in step 2, the uniformly mixed agitation speed is 30-40 r/min;
In the step 2, the stirring speed of the uniform stirring is 30-40 r/min.
4. A method of preparing a zebra coated separator according to any one of claims 1 to 3, comprising the steps of:
step a, coating: coating PVDC slurry on one side of a base film by using an anilox roller, and forming a coating on the base film to obtain a diaphragm;
Step b, extraction: and c, sequentially passing the diaphragm in the step a through 10-15 extraction tanks, and drying to obtain the zebra coating diaphragm, wherein the extractant in the 1 st-3 extraction tanks is a mixture of dimethylacetamide and water, and the extractant in the rest extraction tanks is water.
5. The method according to claim 4, wherein in the step a, the surface of the anilox roller is provided with strip-shaped protrusions for forming a coating.
6. The method according to claim 5, wherein in the step a, a line tangent to the anilox roller and the base film is a tangent line, and a relative movement speed of the tangent line and the base film is 10 to 25m/min.
7. The method according to claim 6, wherein in the step a, the base film is a polyethylene-based film.
8. The method according to claim 7, wherein in the step b, the drying temperature is 50 to 70 ℃ and the drying time is 30 to 40 seconds.
9. The method according to claim 8, wherein in the step b, the extraction is performed at normal temperature;
In said step b, the extraction time in each extraction tank is 5-10 s.
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| CN112909425A (en) * | 2021-01-20 | 2021-06-04 | 河北金力新能源科技股份有限公司 | High-efficiency long-life lithium-sulfur battery diaphragm and preparation method thereof |
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| CN107994186A (en) * | 2017-11-10 | 2018-05-04 | 江苏华富储能新技术股份有限公司 | A kind of lithium battery organo-mineral complexing membrane and preparation method |
| KR20200021435A (en) * | 2018-08-20 | 2020-02-28 | 주식회사 엘지화학 | Method of Manufacturing Separator and Separator manufactured by the same method |
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| CN112909425A (en) * | 2021-01-20 | 2021-06-04 | 河北金力新能源科技股份有限公司 | High-efficiency long-life lithium-sulfur battery diaphragm and preparation method thereof |
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