Separator, preparation method therefor and related secondary battery, battery module, battery pack and device
A separator, comprising a substrate and a coating provided on at least one surface of the substrate are provided. In some embodiments, the coating comprises inorganic particles and organic particles, the organic particles comprise first organic particles and second organic particles both embedded in the inorganic particles and forming protrusions on the surface of the coating; the first organic particles are secondary particles, and the number of the first organic particles in the coating is denoted as A; the second organic particles are primary particles and the number of the second organic particles in the coating is denoted as B; with the separator satisfying: 0.05≤A/B<1. The present application also relates to a method for preparing the separator, as well as a secondary battery comprising the separator, a battery module, a battery pack and a device.
1 . A separator, comprising:
a substrate; and
a coating provided on at least one surface of the substrate; and, wherein
the coating comprises inorganic particles and organic particles, wherein the organic particles comprise first organic particles and second organic particles both embedded in the inorganic particles and forming protrusions on the surface of the coating, wherein
the first organic particles are secondary particles and have a number-average particle size of ≥8 μm, and a number of the first organic particles in the coating is denoted as A; the second organic particles are primary particles and have a number-average particle size of 2 μm-7 μm, and a number of the second organic particles in the coating is denoted as B; with the separator satisfying: 0.05≤A/B<1.
2 . The separator according to claim 1 , wherein the separator satisfies: 0.2≤A/B ≤0.6.
3 . The separator according to claim 1 , wherein the first organic particles have a number-average particle size of 12 μm-25 μm.
4 . The separator according to claim 1 , wherein the second organic particles have a number-average particle size of 3 μm-7 μm.
5 . The separator according to claim 1 , wherein a ratio of a number-average particle size of the first organic particles to that of the second organic particles is ≥2.0.
6 . The separator according to claim 1 , wherein the separator further satisfies:
(1) a mass percentage of the inorganic particles in the coating is ≤75%;
(2) a mass percentage of the first organic particles in the coating is ≥12%; and
(3) a mass percentage of the second organic particles in the coating is ≤10%; and
(4) a separator has a single-sided coating weight per unit area of ≤3.0 g/m 2.
7 . The separator according to claim 6 , wherein the mass percentage of the inorganic particles in the coating is 60% to 75%, the mass percentage of the first organic particles in the coating is 12% to 25%, the mass percentage of the second organic particles in the coating is 2%-10%, and the single-sided coating weight per unit area is 1.5 g/m 2 to 3.0 g/m 2 .
8 . 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.
9 . 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.
10 . The separator according to claim 1 , wherein the second organic particles comprise one or more of a homopolymer or copolymer of an acrylate monomeric unit, a homopolymer or copolymer of an acrylic monomeric unit, a homopolymer or copolymer of a styrene monomeric unit, a polyurethane compound, a rubber compound, and modified compounds of these homopolymers or copolymers.
11 . The separator according to claim 10 , wherein the second organic particles comprise one or more selected from a copolymer of an acrylate monomeric unit and a styrene monomeric unit, a copolymer of an acrylic monomeric unit and a styrene monomeric unit, a copolymer of an acrylic monomeric unit, an acrylate monomeric unit and a styrene monomeric unit, a copolymer of a styrene monomeric unit and an unsaturated nitrile monomeric unit, a copolymer of a styrene monomeric unit, an olefine monomeric unit and an unsaturated nitrile monomeric unit.
12 . The separator according to claim 11 , wherein the second organic particles comprise one or more selected from a copolymer of an acrylate monomeric unit and a styrene monomeric unit and a copolymer of an acrylate monomeric unit, an acrylic monomeric unit, and a styrene monomeric unit, wherein the acrylate monomeric unit comprises isooctyl acrylate or isooctyl methacrylate.
13 . The separator according to claim 12 , wherein the second organic particles comprise one or more selected from a butyl methacrylate-isooctyl methacrylate copolymer, an isooctyl methacrylate-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 acrylate-styrene copolymer, and a butyl methacrylate-isooctyl methacrylate-styrene copolymer.
14 . The separator according to claim 1 , wherein the second organic particles comprise one or more of a butyl acrylate-styrene copolymer, 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 acrylate-styrene copolymer, a butyl methacrylate-isooctyl methacrylate-styrene copolymer, a styrene-acrylonitrile copolymer, a styrene-butadiene-acrylonitrile copolymer, a methyl acrylate-styrene-acrylonitrile copolymer, an isooctyl methacrylate-styrene-acrylonitrile copolymer, a styrene-vinyl acetate copolymer, a styrene-vinyl acetate-pyrrolidone copolymer, and modified compounds of these copolymers.
15 . 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 ).
16 . The separator according to claim 1 , wherein the separator satisfies one or more of the following (1)-(5):
(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 ; and
(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%.
17 . The separator according to claim 1 , wherein the inorganic particles and the organic particles form a non-uniform pore structure in the coating.
18 . The separator according to claim 1 , wherein a spacing between any two adjacent inorganic particles is denoted as L 1 , and a spacing between any inorganic particle and an adjacent organic particle is denoted as L2, with L1<L2.
19 . A method for preparing a separator of claim 1 , comprising the steps of:
(1) providing a substrate;
(2) providing a 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 side of the substrate from step (1) with the coating slurry from step (2) so as to form a coating, and drying same to obtain the separator;
wherein the dried coating comprises the inorganic particles, the first organic particles and the second organic particles which first organic particles and the second organic particles are embedded in the inorganic particles and form protrusions on the surface of the dried coating; the first organic particles are secondary particles, and the number of the first organic particles in the dried coating is denoted as A; the second organic particles are primary particles and the number of the second organic particles in the dried coating is denoted as B; with the separator satisfying: 0.05≤A/B<1.
20 . The method according to claim 19 , wherein the method satisfies one or more of the following (1)-(8):
(1) in step (2), the first organic particles are added in a mass percentage of 12% or more of the total dry weight of the component material;
(2) in step (2), the second organic particles are added in a mass percentage of 10% or less of the total dry weight of the component material;
(3) in step (2), the coating slurry has a solid content of 28%-45%;
(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, optionally 125 LPI-190 LPI;
(5) in step (3), the coating is carried out at a speed of 30 m/min-90 m/min, optionally 50 m/min-70 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.
21 . A secondary battery, comprising a separator according to claim 1 .