Lithium secondary battery separator and method of manufacturing same
Provided is a lithium secondary battery separator including a laminate of a substrate and a porous heat-resistant polyimide film which covers at least one surface of the substrate. The porous heat-resistant polyimide film has pores which are regularly arrayed three-dimensionally and a film thickness of 5-20 μm. Penetration damage to the separator by growth of dendrite-shaped lithium is avoided, and it is also possible to meet a request which is demanded of the lithium secondary battery separator.
1. A lithium secondary battery separator for a lithium secondary battery with an anode composed of lithium metal, the lithium secondary battery separator comprising:
a laminate including
a substrate including a material selected from polypropylene, aramid, cellulose, and polytetrafluoroethylene; and
a porous heat-resistant polyimide film coating at least one surface of the substrate to face toward the anode composed of the lithium metal, to contact the lithium metal of the anode,
the porous heat-resistant polyimide film having a film thickness of 5 μm to 20 μm and a porosity of 70% to 90%,
the porosity being based on, in the porous heat-resistant polyimide film:
three-dimensionally ordered pores constituting 70 vol. % to 80 vol. % of the porous heat-resistant polyimide film, each of the three-dimensionally ordered pores having a pore size of 50 nm to 2500 nm, and
bottleneck-shaped continuous holes, each hole of the bottleneck-shaped continuous holes connecting, among the three-dimensionally ordered pores, pores adjacent to the hole, each hole having a hole size of 20 nm to 1000 nm.
2. A method of manufacturing the lithium secondary battery separator of claim 1 , comprising:
applying a polyimide precursor slurry, which contains uniformly dispersed silica particles having a median particle size selected from a range of 50 nm to 2500 nm, to the at least one surface that is to face toward the anode composed of the lithium metal, the polyimide precursor slurry having a viscosity of 10 poise to 3000 poise and comprising 10 vol. % to 20 vol. % of the silica particles,
drying the slurry to form a silica-polyimide precursor film,
then, subjecting the silica-polyimide precursor film to a cyclodehydration reaction for polyimidization to form a 5 μm to 20 μm-thick silica-polyimide film containing three-dimensionally ordered silica particles constituting 70 vol. % to 80 vol. % of the silica-polyimide film, and
removing the silica particles from the silica-polyimide film to form the porous heat-resistant polyimide film.
3. The method of claim 2 , wherein the polyimide precursor slurry is a polyamide acid solution comprising an acid anhydride component and a diamine component.
4. The method of claim 3 , wherein the substrate is hydrophilized before the applying the polyimide precursor slurry when the substrate is hydrophobic.
5. The method of claim 2 , wherein the substrate is hydrophilized before the applying the polyimide precursor slurry when the substrate is hydrophobic.
6. The lithium secondary battery separator of claim 1 , wherein the porous heat-resistant polyimide film is configured to suppress growth of dendritic lithium on the porous heat-resistant polyimide film.
7. The lithium secondary battery separator of claim 1 , wherein the substrate includes:
the at least one surface including a first surface coated with the porous heat-resistant polyimide film to face toward the anode composed of the lithium metal, and
a second surface opposite to the first surface to face away from the anode and not coated with the porous heat-resistant polyimide film.
8. A lithium secondary battery comprising:
an anode composed of lithium metal; and
a lithium secondary battery separator including:
a laminate including
a substrate including a material selected from polypropylene, aramid, cellulose, and polytetrafluoroethylene; and
a porous heat-resistant polyimide film coating at least one surface of the substrate to face toward the anode composed of the lithium metal, to contact the lithium metal of the anode, having a film thickness of 5 μm to 20 μm and a porosity of 70% to 90%,
the porosity being based on, in the porous heat-resistant polyimide film;
three-dimensionally ordered pores constituting 70 vol. % to 80 vol. % of the porous heat-resistant polyimide film, each of the three-dimensionally ordered pores having a pore size of 50 nm to 2500 nm, and
bottleneck-shaped continuous holes, each hole of the bottleneck-shaped continuous holes connecting, among the three-dimensionally ordered pores, pores adjacent to the hole, each hole having a hole size of 20 nm to 1000 nm.
9. The lithium secondary battery according to claim 8 , wherein the substrate includes:
the at least one surface including a first surface coated with the porous heat-resistant polyimide film to face toward the anode composed of the lithium metal, and
a second surface opposite to the first surface to face away from the anode and not coated with the porous heat-resistant polyimide film.