Separator for electrochemical device and method for manufacturing the same
A separator for an electrochemical device including a heat resistant layer and an adhesive layer and a method for manufacturing the same. The separator uses a heat resistant polymer having a high melting point for a heat resistant layer and shows excellent peel strength between the separator substrate and the heat resistant layer and high adhesion between the separator and an electrode.
1. A separator for an electrochemical device comprising:
a porous substrate;
a heat resistant layer formed on at least one surface of the porous substrate; and
an adhesive layer formed on a surface of the heat resistant layer opposite the porous substrate,
wherein the heat resistant layer comprises inorganic particles and a heat resistant binder resin,
the heat resistant binder resin has a melting point (T m ) of 150° C. or higher,
the adhesive layer consists of a fluorinated binder resin and a non-fluorinated binder resin as adhesive binder resins, and
the non-fluorinated binder resin comprises at least one cyano group-containing copolymer selected from the group consisting of cyanoethyl pullulan, cyanoethyl polyvinyl alcohol, cyanoethyl cellulose, and cyanoethyl sucrose.
2. The separator for the electrochemical device according to claim 1 , wherein the heat resistant layer comprises the heat resistant binder resin in an amount of 1 wt % to 20 wt % based on 100 wt % of the heat resistant layer.
3. The separator for the electrochemical device according to claim 2 , wherein
the heat resistant binder resin is present in an amount larger than 90 wt % based on 100 wt % of the binder resin present in the heat resistant layer.
4. The separator for the electrochemical device according to claim 1 , wherein the heat resistant layer comprises a pore path passing through a thickness direction of the heat resistant layer by one pore or by interconnection of two or more open pores, and
either or both of the fluorinated binder resin and the non-fluorinated binder resin of the adhesive layer are introduced through at least one pore path so that the heat resistant layer is bound with the surface of the porous substrate.
5. The separator for the electrochemical device according to claim 1 , which has a shrinkage of 25% or less in a transverse direction (TD) and machine direction (MD), after it is allowed to stand at 150° C. for 30 minutes.
6. The separator for the electrochemical device according to claim 1 , which has a breakdown voltage of 1.8 kV or higher.
7. The separator for the electrochemical device according to claim 1 , which shows a peel strength of 20 gf/15 mm or more between the heat resistant layer and the porous substrate.
8. The separator for electrochemical device according to claim 1 , wherein the heat resistant binder resin comprises polyacetal, polysulfone (PSF), polyethersulfone (PES), polyetherimide (PEI), polyphenylene sulfide (PPS), polyetherether ketone (PEEK), polyarylate (PA), polycarbonate, polyamideimide (PAI), polyimide (PI), polyamide, fully aromatic polyamide (aramid), polyphenylene oxide, polybutylene terephthalate, polyethylene terephthate, polyether sulfone, polyether ketone or a mixture of at least two of them.
9. The separator for the electrochemical device according to claim 1 , wherein the fluorinated binder resin comprises a polyvinylene fluoride (PVDF)-based polymer resin comprising vinylidene fluoride (VDF) as a unit.
10. The separator for the electrochemical device according to claim 1 , wherein the fluorinated binder resin comprises a copolymer of vinylidene fluoride (VDF) with a comonomer, and the comonomer comprises hexafluoropropylene (HFP), chlorotrifluoroethylene (CTFE), hexafluoroisobutylene, perfluorobutyl ethylene, perfluoropropyl vinyl ether (PPVE), perfluoroethyl vinyl ether (PEVE), perfluromethyl vinyl ether (PMVE), perfluro-2,2-dimethyl-1,3-dioxole (PDD), perfluoro-2-methylene-4-methyl-1,3-dioxolane (PMD) or at least two of them.
11. The separator for the electrochemical device according to claim 1 , wherein the adhesive layer has pores having a rectangular finger-like structure, Bernard cell structure, or a mesoporous structure in a thickness direction.
12. The separator for the electrochemical device according to claim 1 , wherein the non-fluorinated binder resin is present in an amount of 1 wt % to 20 wt % based on 100 wt % of the binder resins in the adhesive layer.
13. The separator for the electrochemical device according to claim 1 , wherein the fluorinated binder resin is concentrated at a surface of the adhesive layer and the non-fluorinated binder resin is concentrated near a surface of the heat resistant layer and wherein the heat resistant layer comprises pores and the non-fluorinated binder resin is partially present to the pores of the heat resistant layer.
14. A method for manufacturing the separator of claim 1 comprising the steps of:
(S10) forming a heat resistant layer on a surface of a porous substrate;
(S20) applying a polymer solution for forming an adhesive layer to a surface of the heat resistant layer opposite the porous substrate; and
(S30) drying the applied polymer solution to form an adhesive layer,
wherein the drying in step (S30) is carried out under a humidifying treatment condition at a relative humidity of 20-50%.
15. The method for manufacturing the separator according to claim 14 , wherein the polymer solution for forming the adhesive layer comprises a fluorinated binder resin, a non-fluorinated binder resin, a solvent and a non-solvent.