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 both embedded in the inorganic particles and forming protrusions on the surface of the coating, the first organic particles have a number-average particle size of ≥8 μm; the second organic particles have a number-average particle size of ≥2 μm, and at least part of the second organic particles comprise a core structure and a shell structure. 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 formed on at least one surface of the substrate;
wherein the coating comprises inorganic particles and organic particles, the inorganic particles form a layer on the at least one surface of the substrate, the organic particles further comprise first organic particles and second organic particles, the first organic particles and second organic particles are partially embedded in the layer formed by the inorganic particles and form protrusions on a surface of the coating;
the first organic particles have a number-average particle size of ≥12 μm;
the second organic particles have a number-average particle size of 3 μm to 8 μm, and each one of at least a portion of the second organic particles has a core-shell structure comprising a core and a shell;
the core and the shell both comprise a copolymer of an acrylate monomeric unit and a styrene monomeric unit, wherein the acrylate monomeric unit comprises isooctyl acrylate or isooctyl methacrylate; and
a glass transition temperature of the shell is higher than a glass transition temperature of the core.
2 . The separator according to claim 1 , wherein the first organic particles have a number-average particle size of 15 μm-25 μm.
3 . The separator according to claim 1 , wherein the second organic particles have a number-average particle size of 3 μm-6 μm.
4 . The separator according to claim 1 , wherein a ratio of the number-average particle size of the first organic particles to the number-average particle size of the second organic particles is ≥2.
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 first organic particles comprise one or more from the group consisting 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 any combinations thereof.
8 . The separator according to claim 1 , wherein the first organic particles comprise a polymer selected from the group consisting 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 any combination thereof.
9 . The separator according to claim 1 , wherein the copolymer of the core and the shell is selected from the group consisting 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, and any combination thereof.
10 . The separator according to claim 1 , wherein the inorganic particles comprise a metal compound selected from the group consisting of boehmite (γ-AlOOH), aluminum oxide (Al2O3), barium sulfate (BaSO4), magnesium oxide (MgO), magnesium hydroxide (Mg(OH)2), silicon dioxide (SiO2), tin dioxide (SnO2), titanium oxide (TiO2), calcium oxide (CaO), zinc oxide (ZnO), zirconium oxide (ZrO2), yttrium oxide (Y2O3), nickel oxide (NiO), cerium oxide (CeO2), zirconium titanate (SrTiO3), barium titanate (BaTiO3), magnesium fluoride (MgF2), and any combination thereof.
11 . The separator according to claim 1 , wherein:
(1) a mass percentage of the inorganic particles in the coating is ≤70%;
(2) a mass percentage of the first organic particles in the coating is ≥12%;
(3) a mass percentage of the second organic particles in the coating is ≤10%; and
(4) the separator has a single-sided coating weight per unit area of ≤3.0 g/m 2 .
12 . The separator according to claim 1 , wherein:
(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%.
13 . The separator according to claim 1 , wherein the inorganic particles and the organic particles form a non-uniform pore structure in the coating.
14 . 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, wherein L1<L2.
15 . A secondary battery, comprising a positive electrode plate, a negative electrode plate, a separator disposed between the positive electrode plate and the negative electrode plate, and an electrolyte, wherein the separator comprises:
a substrate; and
a coating formed on at least one surface of the substrate;
wherein the coating comprises inorganic particles and organic particles, the inorganic particles form a layer on the at least one surface of the substrate, the organic particles further comprise first organic particles and second organic particles, the first organic particles and second organic particles are partially embedded in the layer formed by the inorganic particles and form protrusions on a surface of the coating;
the first organic particles have a number-average particle size of 12 μm to 25 μm;
the second organic particles have a number-average particle size of 3 μm to 8 μm, and each one of at least a portion of the second organic particles has a core-shell structure comprising a core and a shell;
the core and the shell both comprise a copolymer of an acrylate monomeric unit and a styrene monomeric unit, wherein the acrylate monomeric unit comprises isooctyl acrylate and isooctyl methacrylate; and
a glass transition temperature of the shell is higher than a glass transition temperature of the core.
16 . The separator according to claim 9 , wherein the copolymer of the core and shell is a butyl methacrylate-isooctyl methacrylate-styrene copolymer.
17 . The secondary battery according to claim 15 , wherein the copolymer of the core and shell is a butyl methacrylate-isooctyl methacrylate-styrene copolymer.
18 . 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 inorganic particles form a layer on the at least one surface of the substrate, the organic particles further comprise first organic particles and second organic particles, the first organic particles and second organic particles are partially embedded in the layer formed by the inorganic particles and form protrusions on a surface of the coating;
the first organic particles have a number-average particle size of ≥12 μm;
the second organic particles have a number-average particle size of 3 μm to 8 μm, and each one of at least a portion of the second organic particles has a core-shell structure comprising a core and a shell;
the core and the shell of the second organic particles comprise a copolymer of an acrylate monomeric unit and a styrene monomeric unit, wherein the acrylate monomeric unit comprises isooctyl acrylate or isooctyl methacrylate;
a glass transition temperature of the shell is higher than a glass transition temperature of the core; and
the inorganic particles and the organic particles form a non-uniform pore structure in the coating.