Separator for lithium secondary battery, and lithium secondary battery comprising same
The present invention relates to a separator for a lithium secondary battery, and a lithium secondary battery including the same. The separator includes a porous substrate and a coating layer on at least one surface of the porous substrate, wherein the coating layer includes a binder including a (meth)acrylic copolymer including a first structural unit derived from (meth)acrylamide, a second structural unit derived from (meth)acrylonitrile, and a third structural unit derived from (meth)acrylamidosulfonic acid, a (meth)acrylamidosulfonic acid salt or a combination thereof; first inorganic particles; and second inorganic particles, wherein the average diameter of the first inorganic particles is 400 nm to 600 nm, and the average diameter of the second inorganic particles is smaller than the average diameter of the first inorganic particles.
1. A separator for a lithium secondary battery, comprising
a porous substrate and a coating layer on at least one surface of the porous substrate,
wherein the coating layer comprises
a binder including a (meth)acrylic copolymer of a first structural unit derived from (meth)acrylamide, a second structural unit derived from (meth)acrylonitrile, and a third structural unit derived from (meth)acrylamidosulfonic acid, (meth)acrylamidosulfonic acid salt, or a combination thereof, and wherein the first structural unit derived from (meth)acrylamide is represented by Chemical Formula 1, the second structural unit derived from (meth)acrylonitrile is represented by Chemical Formula 2, and the third structural unit derived from (meth)acrylamidosulfonic acid, (meth)acrylamidosulfonic acid salt, or a combination thereof is represented by one of Chemical Formula 3, Chemical Formula 4, Chemical Formula 5, and a combination thereof:
wherein, in Chemical Formula 1 to Chemical Formula 5,
R 1 is hydrogen or a methyl group,
R 2 , R 3 , R 4 and R 5 are each independently hydrogen or a C1 to C3 alkyl group,
L 1 , L 3 , L 5 and L 7 are each independently —C(═O)—, —C(═O)O—, —OC(═O)—, —O—, or —C(═O)NH—,
L 2 , L 4 , L 6 and L 8 are each independently a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, or a substituted or unsubstituted C3 to C20 heterocyclic group,
x and y are each independently an integer of 0 to 2,
a, b, c, d, e, and f are each independently an integer of 0 to 2, and M + is an alkali metal;
first inorganic particles; and
second inorganic particles;
wherein the average diameter of the first inorganic particles is 400 nm to 600 nm, the average diameter of the second inorganic particles is smaller than the average diameter of the first inorganic particles, and the second inorganic particles are included in an amount of 30 wt. % to 60 wt. % based on the total amount of the first inorganic particles and the second inorganic particles.
2. The separator of claim 1 , wherein the second inorganic particles have an average particle diameter (D50) of 50 nm to 200 nm.
3. The separator of claim 1 , wherein a volume ratio of the first inorganic particles and the second inorganic particles is 1.4:1 to 1.2:1.
4. The separator of claim 1 , wherein the first inorganic particles and the second inorganic particles may each independently include Al 2 O 3 , SiO 2 , TiO 2 , SnO 2 , CeO 2 , MgO, NiO, CaO, GaO, ZnO, ZrO 2 , Y 2 O 3 , SrTiO 3 , BaTiO 3 , Mg(OH) 2 , boehmite, and a combination thereof.
5. The separator of claim 1 , wherein a weight ratio the binder:a sum of the first inorganic particles and second inorganic particles is 1:15 to 1:50.
6. The separator of claim 1 , wherein the (meth)acrylic copolymer has a glass transition temperature of 150° C. to 180° C.
7. The separator of claim 1 , wherein the first structural unit is included in an amount of 55 mol % to 90 mol % based on 100 mol % of the (meth)acrylic copolymer and the second structural unit and third structural unit are each independently included in 5 mol % to 40 mol % based on 100 mol % of the (meth)acrylic copolymer.
8. The separator of claim 1 , wherein
the second structural unit derived from (meth)acrylonitrile is included in an amount of 5 mol % to 40 mol % based on 100 mol % of the (meth)acrylic copolymer, and
the third structural unit derived from (meth)acrylamidosulfonic acid, (meth)acrylamidosulfonic acid salt, or a combination thereof is included in an amount of 5 mol % to 10 mol % based on 100 mol % of the (meth)acrylic copolymer.
9. The separator of claim 1 , wherein
the first structural unit derived from (meth)acrylamide is included in an amount of 80 mol % to 85 mol % based on 100 mol % of the (meth)acrylic copolymer,
the second structural unit derived from (meth)acrylonitrile is included in an amount of 10 mol % to 15 mol % based on 100 mol % of the (meth)acrylic copolymer, and
the third structural unit derived from (meth)acrylamidosulfonic acid, (meth)acrylamidosulfonic acid salt, or a combination thereof is included in an amount of 5 to 10 mol % based on 100 mol % of the (meth)acrylic copolymer.
10. The separator of claim 1 , wherein the (meth)acrylic copolymer has a weight average molecular weight of 200,000 to 700,000.
11. The separator of claim 1 , wherein the (meth)acrylic copolymer is included in an amount of 1 wt % to 5 wt % based on a total amount of the coating layer.
12. The separator of claim 1 , wherein the coating layer has a thickness of 1 μm to 5 μm.
13. The separator of claim 1 , wherein the separator has a moisture content of less than or equal to 800 ppm.
14. A lithium secondary battery comprising a positive electrode, a negative electrode, and the separator for a lithium secondary battery of claim 1 between the positive electrode and the negative electrode.