Secondary battery with improved storage characteristics and method for manufacturing the same
View Patent ↗Provided is a secondary battery comprising a separator having an inorganic layer wherein active sites of inorganic particles in the inorganic layer are modified into non-reactive sites. Use of the separator leads to improvements in wettability of an electrolyte and thermoelectric stability and storage characteristics of the secondary battery. Provided is also a method of manufacturing the same secondary battery.
1. An organic/inorganic composite separator for a secondary battery comprising:
an organic layer selected from the group consisting of a polyethylene layer, a polypropylene layer, a polyethylene/polypropylene bilayer, a polyethylene/polypropylene/polyethylene trilayer, a polypropylene/polyethylene/polypropylene trilayer, and an organic fiber filter paper layer; and
an inorganic layer comprising inorganic particles and a modifying agent,
wherein the inorganic particles comprise an OH group and at least one selected from the group consisting of alumina, titanium oxide, zirconium oxide, zinc oxide, silicon dioxide, and magnesium oxide;
the modifying agent comprises at least one functional group selected from the group consisting of phosphonate, phosphate, phosphonic acid, and carboxylic acid;
a molar ratio of the OH group of the inorganic particles and the functional group of the inorganic modifying agent is from 5:1to 10:1; and
at least one surface of the organic layer is coated with the inorganic layer.
2. The separator according to claim 1 , wherein the modifying agent comprises at least one selected from the group consisting of phenyl phosphonic acid, methyl phosphonic acid, triphenyl phosphate, dimethylmethyl phosphonate, diethylmethyl phosphonate, octanoic acid, gallic acid, and aminobenzoic acid.
3. The separator according to claim 1 , wherein the inorganic layer is formed on at least a surface of the organic layer by preparing slurry containing the inorganic particles, the modifying agent, a solvent, and a resin, and coating the surface of the organic layer with the slurry.
4. The separator according to claim 3 , wherein the slurry is prepared by stirring the inorganic particles and the modifying agent in the solvent to modify the inorganic particles and then mixing the modified inorganic particles and the solvent with the resin.
5. A method for manufacturing a an organic/inorganic composite separator, the method comprising the steps of:
preparing slurry comprising 1 wt% to 20 wt% of a modifying agent, inorganic particles, a solvent, and a resin, wherein the inorganic modifying agent comprises at least one functional group selected from the group consisting of phosphonate, phosphate, phosphonic acid, and carboxylic acid, and the inorganic particles comprise at least one selected from the group consisting of alumina, titanium oxide, zirconium oxide, zinc oxide, silicon dioxide, and magnesium oxide; and
forming an inorganic layer by coating at least a surface of an organic layer with the slurry, wherein the organic layer is a layer selected from the group consisting of a polyethylene layer, a polypropylene layer, a polyethylene/polypropylene bilayer, a polyethylene/polypropylene/polyethylene trilayer, a polypropylene/polyethylene/polypropylene trilayer, and an organic fiber filter paper layer.
6. The method according to claim 5 , wherein the modifying agent comprises at least one selected from the group consisting of phenyl phosphonic acid, methyl phosphonic acid, triphenyl phosphate, dimethylmethyl phosphonate, diethylmethyl phosphonate, octanoic acid, gallic acid, and aminobenzoic acid.
7. The method according to claim 5 , wherein the step of preparing slurry comprises the steps of:
modifying the inorganic particles by stirring a solution containing the modifying agent and the inorganic particles until a molar ratio of the functional group of the modifying agent and an OH group included in the inorganic particles becomes 1:5 to 1:10; and
mixing the resin to the solution containing the modifying inorganic particles.