Separator, preparation method therefor and related secondary battery, battery module, battery pack and device
The present application relates to a separator, comprising a substrate and a coating formed on at least one surface of the substrate; wherein the coating comprises inorganic particles and organic particles, the organic particles comprise first organic particles and second organic particles; the first organic particles and the second organic particles are embedded in the inorganic particles and form protrusions on the surface of the coating; the first organic particles have a number-average particle size of >10 μm, and the second organic particles have a number-average particle size of 2 μm-10 μm. The present application also relates to a secondary battery comprising the separator, a device comprising the secondary battery and a method for preparing the separator.
1. A separator, comprising:
a substrate; and
a coating provided on at least one surface of the substrate;
wherein the coating comprises inorganic particles and organic particles, the organic particles comprise first organic particles and second organic particles;
the first organic particles and the second organic particles are embedded in the inorganic particles and form protrusions on a surface of the coating;
the first organic particles have a number-average particle size of 10 μm-25 μm, and the second organic particles have a number-average particle size of 2 μm-8 μm, wherein the number-average particle size refers to an arithmetic mean of the particle size of the first and second organic particles that is obtained by counting the respective number of the first and second organic particles in the coating;
the inorganic particles have a volume-average particle size Dv50 of 0.5 μm-2.5 μm, a mass percentage of the inorganic particles in the coating is ≤70% based on a total mass of the coating, a mass percentage of the first organic particles in the coating is ≥12% based on a total mass of the coating, a mass percentage of the second organic particles in the coating is ≤10% based on a total mass of the coating;
the second organic particles comprise one or more of a butyl methacrylate-isooctyl methacrylate copolymer, an isooctyl methacrylate-styrene copolymer, a methacrylate-methacrylic acid-styrene copolymer, a methyl acrylate-isooctyl methacrylate-styrene copolymer, a butyl acrylate-isooctyl acrylate-styrene copolymer, a butyl acrylate-isooctyl methacrylate-styrene copolymer, a butyl methacrylate-isooctyl methacrylate-styrene copolymer, a butyl methacrylate-isooctyl acrylate-styrene copolymer, an isooctyl methacrylate-styrene-acrylonitrile copolymer, and a styrene-vinyl acetate-pyrrolidone copolymer.
2. The separator according to claim 1 , wherein the first organic particles have a number-average particle size of 12 μm-25 μm.
3. The separator according to claim 1 , wherein the second organic particles have a number-average particle size of 4.8 μm-8 μm.
4. The separator according to claim 1 , wherein a ratio of the number-average particle size of the first organic particles to that of the second organic particles is 2.1 to 7.5.
5. The separator according to claim 1 , wherein the first organic particles are secondary particles.
6. The separator according to claim 1 , wherein the second organic particles are primary particles.
7. The separator according to claim 1 , wherein the separator has a single-sided coating weight per unit area of ≤3.0 g/m 2 .
8. The separator according to claim 1 , wherein the volume-average particle size Dv50 of the inorganic particles is 1.5 μm-2.5 μm.
9. The separator according to claim 1 , wherein:
(1) a mass percentage of the inorganic particles in the coating is 60%-70%;
(2) the mass percentage of the first organic particles in the coating is 12%-30%; and
(3) a mass percentage of the second organic particles in the coating is 2%-10%.
10. The separator according to claim 1 , wherein the first organic particles comprise one or more of a homopolymer or copolymer of a fluorine-containing olefine monomeric unit, a homopolymer or copolymer of an olefine monomeric unit, a homopolymer or copolymer of an unsaturated nitrile monomeric unit, a homopolymer or copolymer of an alkylene oxide monomeric unit, and modified compounds of these homopolymers or copolymers.
11. The separator according to claim 1 , wherein the first organic particles comprise one or more of a vinylidene fluoride-trifluoroethylene copolymer, a vinylidene fluoride-hexafluoropropylene copolymer, a vinylidene fluoride-trifluoroethylene-hexafluoropropylene copolymer, a vinylidene fluoride-hexafluoropropylene-acrylic acid copolymer, a vinylidene fluoride-hexafluoropropylene-acrylate copolymer, and modified compounds of these copolymers.
12. The separator according to claim 1 , wherein the second organic particles comprise one or more of a butyl methacrylate-isooctyl methacrylate-styrene copolymer and a styrene-vinyl acetate-pyrrolidone copolymer.
13. The separator according to claim 1 , wherein the inorganic particles comprise one or more of boehmite (γ-AlOOH), aluminum oxide (Al 2 O 3 ), barium sulfate (BaSO 4 ), magnesium oxide (MgO), magnesium hydroxide (Mg(OH) 2 ), silicon dioxide (SiO 2 ), tin dioxide (SnO 2 ), titanium oxide (TiO 2 ), calcium oxide (CaO), zinc oxide (ZnO), zirconium oxide (ZrO 2 ), yttrium oxide (Y 2 O 3 ), nickel oxide (NiO), cerium oxide (CeO 2 ), zirconium titanate (SrTiO 3 ), barium titanate (BaTiO 3 ), and magnesium fluoride (MgF 2 ).
14. The separator according to claim 1 , wherein the separator satisfies:
(1) the separator has an air permeability of 100 s/100 mL-300 s/100 mL;
(2) the separator has a transverse tensile strength (MD) of 1500 kgf/cm 2 -3000 kgf/cm 2 ;
(3) the separator has a longitudinal tensile strength (TD) of 1000 kgf/cm 2 -2500 kgf/cm 2 ;
(4) the separator has a transverse elongation at break of 50%-200%; and
(5) the separator has a longitudinal elongation at break of 50%-200%.
15. The separator according to claim 1 , wherein the inorganic particles and the organic particles form a non-uniform pore structure in the coating.
16. The separator according to claim 1 , wherein a spacing between any two adjacent inorganic particles is denoted as L1, and a spacing between any inorganic particle and an adjacent organic particle is denoted as L2, with L1<L2.
17. A secondary battery, comprising a separator according to claim 1 .
18. A method for preparing a separator, comprising:
(1) providing a substrate;
(2) providing a coating slurry, the coating slurry comprising a component material and a solvent, wherein the component material comprises inorganic particles and organic particles, and the organic particles comprise first organic particles and second organic particles; and
(3) coating at least one surface of the substrate from step (1) with the coating slurry from step (2) so as to form a coating, and drying the same to obtain the separator;
wherein the separator comprises the substrate and the coating provided on at least one surface of the substrate; and the coating comprise the inorganic particles, the first organic particles and the second organic particles; the first organic particles and the second organic particles are embedded in the inorganic particles and form protrusions on a surface of the coating; and the first organic particles have a number-average particle size of 10 μm to 25 μm, and the second organic particles have a number-average particle size of 2 μm-8 μm,
wherein the number-average particle size refers to an arithmetic mean of the particle size of the first and second organic particles that is obtained by counting the respective number of the first and second organic particles in the coating, and
wherein the inorganic particles have a volume-average particle size Dv50 of 0.5 μm-2.5 μm, a mass percentage of the inorganic particles in the coating is ≤70% based on a total mass of the coating, a mass percentage of the first organic particles in the coating is 12% to 30% based on a total mass of the coating, and a mass percentage of the second organic particles in the coating is 2% to 10% based on the total mass of the coating;
wherein the second organic particles comprise one or more of a butyl methacrylate-isooctyl methacrylate copolymer, an isooctyl methacrylate-styrene copolymer, a methacrylate-methacrylic acid-styrene copolymer, a methyl acrylate-isooctyl methacrylate-styrene copolymer, a butyl acrylate-isooctyl acrylate-styrene copolymer, a butyl acrylate-isooctyl methacrylate-styrene copolymer, a butyl methacrylate-isooctyl methacrylate-styrene copolymer, a butyl methacrylate-isooctyl acrylate-styrene copolymer, an isooctyl methacrylate-styrene-acrylonitrile copolymer, and a styrene-vinyl acetate-pyrrolidone copolymer.
19. The preparation method according to claim 18 , wherein the method satisfies:
(1) in step (2), the first organic particles are added in a mass percentage of 15% to 25% of a total dry weight of the component material;
(2) in step (2), the second organic particles are added in a mass percentage of 3% to 7% of the total dry weight of the component material;
(3) in step (2), the coating slurry has a solid content of 28%-45% by weight;
(4) in step (3), the coating is carried out using a coating machine, which comprises a gravure roller having a number of lines of 100 LPI-300 LPI;
(5) in step (3), the coating is carried out at a speed of 30 m/min-90 m/min;
(6) in step (3), the coating is carried out at a line speed ratio of 0.8-2.5;
(7) in step (3), the drying is carried out at a temperature of 40° C. to 70° C.; and
(8) in step (3), the drying is carried out for a period of 10 s-120 s.
20. A separator, comprising:
a substrate; and
a coating provided on at least one surface of the substrate;
wherein the coating comprises inorganic particles and organic particles, the organic particles comprise first organic particles and second organic particles;
the first organic particles and the second organic particles are embedded in the inorganic particles and form protrusions on a surface of the coating;
the second organic particles comprise one or more of a butyl methacrylate-isooctyl methacrylate copolymer, an isooctyl methacrylate-styrene copolymer, a methacrylate-methacrylic acid-styrene copolymer, a methyl acrylate-isooctyl methacrylate-styrene copolymer, a butyl acrylate-isooctyl acrylate-styrene copolymer, a butyl acrylate-isooctyl methacrylate-styrene copolymer, a butyl methacrylate-isooctyl methacrylate-styrene copolymer, a butyl methacrylate-isooctyl acrylate-styrene copolymer, an isooctyl methacrylate-styrene-acrylonitrile copolymer, and a styrene-vinyl acetate-pyrrolidone copolymer;
the first organic particles have a number-average particle size of 10 μm to 25 μm, and the second organic particles have a number-average particle size of 2 μm-8 μm, wherein the number-average particle size refers to an arithmetic mean of the particle size of the first and second organic particles that is obtained by counting the respective number of the first and second organic particles in the coating, a ratio of the number-average particle size of the first organic particles to that of the second organic particles is 2.1 to 7.5;
the inorganic particles have a volume-average particle size Dv50 of 0.5 μm-2.5 μm, a mass percentage of the inorganic particles in the coating is 60%-70% based on a total mass of the coating, a mass percentage of the first organic particles in the coating is 12% to 30% based on a total mass of the coating, and a mass percentage of the second organic particles in the coating is 2% to 10% based on the total mass of the coating; and
the separator has a single-sided coating weight per unit area of ≤3.0 g/m 2 .