Method for manufacturing separator, separator manufactured by the method and method for manufacturing electrochemical device including the separator
View Patent ↗Disclosed is a method for manufacturing a separator. The method includes (S1) preparing a porous planar substrate having a plurality of pores, (S2) preparing a slurry containing inorganic particles dispersed therein and a polymer solution including a first binder polymer and a second binder polymer in a solvent, and coating the slurry on at least one surface of the porous substrate, (S3) spraying a non-solvent incapable of dissolving the second binder polymer on the slurry, and (S4) simultaneously removing the solvent and the non-solvent by drying. According to the method, a separator with good bindability to electrodes can be manufactured in an easy manner. In addition, problems associated with the separation of inorganic particles in the course of manufacturing an electrochemical device can be avoided.
1. A method for manufacturing a separator, comprising steps:
(S1) preparing a porous, planar substrate having a plurality of pores;
(S2) preparing a slurry containing inorganic particles dispersed therein and a polymer solution comprising a first binder polymer and a second binder polymer in a solvent, and coating the slurry on at least one surface of the porous substrate so as to create a slurry coating layer;
(S3) spraying a non-solvent incapable of dissolving the second binder polymer on the slurry, such that the non-solvent sprayed on the slurry coating layer promotes phase separation of the second binder polymer in the slurry to allow a larger amount of the second binder polymer to be distributed on the surface of the slurry coating layer; and
(S4) simultaneously removing the solvent and the non-solvent by drying;
wherein steps (s1) to (S4) are suitable for manufacturing a separator for an electrochemical device.
2. The method according to claim 1 , wherein the porous substrate is a porous polyolefin membrane.
3. The method according to claim 1 , wherein the porous substrate has a thickness of 1 to 100 μm.
4. The method according to claim 1 , wherein the inorganic particles have an average particle diameter of 0.001 to 10 μm.
5. The method according to claim 1 , wherein the inorganic particles are selected from the group consisting of inorganic particles having a dielectric constant of at least 5, inorganic particles having the ability to transport lithium ions, and mixtures thereof.
6. The method according to claim 5 , wherein the inorganic particles having a dielectric constant of at least 5 are selected from the group consisting of BaTiO 3 , Pb(Zr,Ti)O 3 (PZT), Pb 1-x La x Zr 1-y Ti y O 3 (PLZT, 0<x<1, 0<y<1), Pb(Mg 1/3 Nb 2/3 )O 3 —PbTiO 3 (PMN-PT), hafnia (HfO 2 ), SrTiO 3 , SnO 2 , CeO 2 , MgO, NiO, CaO, ZnO, ZrO 2 , Y 2 O 3 , Al 2 O 3 , SiC, TiO 2 particles, and mixtures thereof.
7. The method according to claim 5 , wherein the inorganic particles having the ability to transport lithium ions are selected from the group consisting of lithium phosphate (Li 3 PO 4 ), lithium titanium phosphate (Li x Ti y (PO 4 ) 3 , 0<x<2, 0<y<3), lithium aluminum titanium phosphate (Li x Al y Ti z (PO 4 ) 3 , 0<x<2, 0<y<1, 0<z<3), (LiAlTiP) x O y type glass (0<x<4, 0<y<13), lithium lanthanum titanate (Li x La y TiO 3 , 0<x<2, 0<y<3), lithium germanium thiophosphate (Li x Ge y P x S w , 0<x<4, 0<y<1, 0<z<1, 0<w<5), lithium nitride (Li x N y , 0<x<4, 0<y<2), SiS 2 type glass (Li x Si y S x , 0<x<3, 0<y<2, 0<z<4), P 2 S 5 type glass particles (Li x P y S x , 0<x<3, 0<y<3, 0<z<7), and mixtures thereof.
8. The method according to claim 1 , wherein the first binder polymer is a polymer having cyano groups.
9. The method according to claim 8 , wherein the polymer having cyano groups is selected from the group consisting of cyanoethylpullulan, cyanoethyl polyvinyl alcohol, cyanoethyl cellulose, polycyanoacrylate, cyanoethyl sucrose and mixtures thereof.
10. The method according to claim 1 , wherein the first binder polymer is polyacrylamide-co-acrylate.
11. The method according to claim 1 , wherein the solvent has a solubility parameter difference of 5.0 Mpa 0.5 or less from those of the first binder polymer and the second binder polymer.
12. The method according to claim 11 , wherein the solvent is selected from the group consisting of acetone, N,N-dimethylacetamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, methyl ethyl ketone and mixtures thereof.
13. The method according to claim 1 , wherein the second binder polymer is selected from the group consisting of polyvinylidene fluoride-co-hexafluoropropylene, polyvinylidene fluoride-co-trichloroethylene, polymethyl methacrylate and mixtures thereof.
14. The method according to claim 1 , wherein the difference in solubility parameter between the non-solvent and the second binder polymer is 8.0 Mpa 0.5 or more.
15. The method according to claim 14 , wherein the non-solvent is selected from the group consisting of water, methanol, ethanol and mixtures thereof.
16. The method according to claim 1 , wherein the first binder polymer and the second binder polymer is in a weight ratio of 75:25 to 10:90.
17. The method according to claim 1 , wherein the inorganic particles and the binder polymers is in a weight ratio of 50:50 to 99:1.
18. A method for manufacturing an electrochemical device, the method comprising interposing a separator manufactured by the method according to claim 1 between a cathode and an anode, followed by lamination.
19. The method according to claim 18 , wherein the electrochemical device is a lithium secondary battery.