Electrolyte membrane for lithium battery, lithium battery using the electrolyte membrane, and method of preparing the electrolyte membrane
An electrolyte membrane for a lithium battery, the electrolyte membrane including: a matrix including a polymerization product of a (meth)acrylate monomer composition; and a porous metal-organic framework dispersed in the matrix, wherein the metal-organic framework includes a crystalline compound including a metal ion or metal ion cluster which is chemically bound to an organic ligand, and a liquid electrolyte including a lithium salt and a nonaqueous organic solvent.
1. An electrolyte membrane for a lithium battery, the electrolyte membrane comprising:
a matrix comprising a polymerization product of a (meth)acrylate monomer composition; and
a porous metal-organic framework dispersed in the matrix, wherein the metal-organic framework comprises
a compound comprising a metal ion or metal ion cluster chemically bound to an organic ligand wherein the metal ion is Ti 4+ , Y 3+ , or a combination thereof, wherein the organic ligand is a substituted or unsubstituted aromatic polycarboxylic acid ligand, and
a liquid electrolyte comprising a lithium salt and a nonaqueous organic solvent.
2. The electrolyte membrane of claim 1 , wherein the liquid electrolyte is retained in the pores of the metal-organic framework.
3. The electrolyte membrane of claim 2 , wherein the pores have an average diameter of about 0.5 nanometers to about 3 nanometers.
4. The electrolyte membrane of claim 1 , wherein the (meth)acrylate monomer composition comprises a poly(ethyleneglycol) diacrylate, a poly(propylene glycol) diacrylate, a poly(ethyleneglycol) dimethacrylate, a poly(propylene glycol) dimethacrylate, a poly(ethyleneglycol)urethane diacrylate, a poly(ethyleneglycol)urethane dimethacrylate, a polyester diacrylate, a polyester dimethacrylate, a poly(ethyleneglycol)urethane triacrylate, a poly(ethyleneglycol)urethane trimethacrylate, a trimethylolpropane triacrylate, a trimethylolpropane trimethacrylate, an ethoxy-substituted trimethylolpropane triacrylate, a propoxy-substituted trimethylolpropane triacrylate, glyceryl triacrylate, glyceryl trimethacrylate, tetramethylolpropane tetraacrylate, di(trimethylolpropane) tetraacrylate, or combination thereof.
5. The electrolyte membrane of claim 1 , wherein the organic ligand is a substituted or unsubstituted aromatic dicarboxylic acid ligand, a substituted or unsubstituted aromatic tricarboxylic acid ligand, or a combination thereof.
6. The electrolyte membrane of claim 1 , wherein the lithium salt is LiClO 4 , LiCF 3 SO 3 , LiBF 4 , LiN(CF 3 SO 2 ) 2 , LiPF 6 , LiAsF 6 , LiSbF 6 , LiPF 3 (CF 2 CF 3 ) 3 , or a combination thereof.
7. The electrolyte membrane of claim 1 , wherein the nonaqueous organic solvent is ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, 1-fluoroethylene carbonate, sulfolane, 1,3-dioxane, γ-butyrolactone, or a combination thereof.
8. The electrolyte membrane of claim 1 , wherein the organic ligand is a substituted or unsubstituted C6 to C30 aromatic dicarboxylic acid ligand, a substituted or unsubstituted C6 to C30 aromatic tricarboxylic acid ligand, or a combination thereof.
9. A lithium battery comprising:
a positive electrode;
a negative electrode; and
an electrolyte,
wherein the electrolyte is a membrane comprising
a matrix comprising a polymerization product of a (meth)acrylate monomer composition, and
a porous metal-organic framework dispersed in the matrix, wherein the metal-organic framework comprises
a compound comprising a metal ion or metal ion cluster which is chemically bound to an organic ligand wherein the metal ion is Zn 2+ , Ti 4+ , V 4+ , V 3+ , V 2+ , Y 3+ , Zr 4+ , a trivalent lanthanide, or a combination thereof, and wherein the organic ligand is a substituted or unsubstituted aromatic polycarboxylic acid ligand, and
a liquid electrolyte comprising a lithium salt and a nonaqueous organic solvent.
10. The electrolyte membrane of claim 1 , wherein the organic ligand chemically bonds adjacent metal ions or metal ion clusters.
11. The electrolyte membrane of claim 1 , wherein a weight ratio between the metal-organic framework and the (meth)acrylate composition is 1:0.5 to about 1:1.
12. The electrolyte membrane of claim 11 , wherein the matrix is a polymerization product of a (meth)acrylate monomer composition consisting of a di(meth)acrylate, and wherein the di(meth)acrylate is a poly(ethyleneglycol) diacrylate, a poly(propyleneglycol) diacrylate, a poly(ethyleneglycol) dimethacrylate, a poly(propyleneglycol) dimethacrylate, or a combination thereof.
13. The electrolyte membrane of claim 12 , wherein the metal ion is Y 3+ .
14. The electrolyte membrane of claim 8 , wherein a weight ratio between the metal-organic framework and the (meth)acrylate composition is 1:0.5 to about 1:1.
15. The electrolyte membrane of claim 1 , wherein the metal ion is Y 3+ .
16. The electrolyte membrane of claim 1 , wherein the metal ion is Ti 4+ .
17. The lithium battery of claim 9 , wherein the organic ligand is an unsubstituted C6 to C30 aromatic dicarboxylic acid ligand, an unsubstituted C6 to C30 aromatic tricarboxylic acid ligand, or a combination thereof.
18. The lithium battery of claim 9 , wherein the liquid electrolyte is retained in the pores of the metal-organic framework.
19. The lithium battery of claim 18 , wherein the pores have an average diameter of about 0.5 nanometers to about 3 nanometers.
20. The lithium battery of claim 9 , wherein the (meth)acrylate monomer composition comprises a poly(ethyleneglycol) diacrylate, a poly(propylene glycol) diacrylate, a poly(ethyleneglycol) dimethacrylate, a poly(propylene glycol) dimethacrylate, a poly(ethyleneglycol)urethane diacrylate, a poly(ethyleneglycol)urethane dimethacrylate, a polyester diacrylate, a polyester dimethacrylate, a poly(ethyleneglycol)urethane triacrylate, a poly(ethyleneglycol)urethane trimethacrylate, a trimethylolpropane triacrylate, a trimethylolpropane trimethacrylate, an ethoxy-substituted trimethylolpropane triacrylate, a propoxy-substituted trimethylolpropane triacrylate, glyceryl triacrylate, glyceryl trimethacrylate, tetramethylolpropane tetraacrylate, di(trimethylolpropane)tetraacrylate, or a combination thereof.
21. The lithium battery of claim 9 , wherein the organic ligand is a substituted or unsubstituted aromatic dicarboxylic acid ligand, a substituted or unsubstituted aromatic tricarboxylic acid ligand, or a combination thereof.
22. A method of manufacturing an electrolyte membrane for a lithium battery, the method comprising:
providing a porous metal-organic framework;
mixing the metal-organic framework, a (meth)acrylate monomer composition, and a solvent to obtain a combination;
coating the mixture on a substrate to form a coated layer;
polymerizing the coated layer to provide a polymerized layer; and impregnating the polymerized layer with a liquid electrolyte comprising a lithium salt and a nonaqueous organic solvent to manufacture the electrolyte membrane, wherein the electrolyte membrane comprises
a matrix comprising a polymerization product of the (meth)acrylate monomer composition; and
the metal-organic framework dispersed in the matrix, wherein the metal-organic framework comprises
a compound comprising a metal ion or metal ion cluster chemically bound to an organic ligand wherein the metal ion is Ti 4+ , Y 3+ , or a combination thereof, wherein the organic ligand is a substituted or unsubstituted aromatic polycarboxylic acid ligand, and
wherein the liquid electrolyte comprises the lithium salt and the nonaqueous organic solvent.
23. The method of claim 22 , wherein the (meth)acrylate monomer composition comprises a poly(ethyleneglycol) diacrylate, a poly(propylene glycol) diacrylate, a poly(ethyleneglycol) dimethacrylate, a poly(propylene glycol) dimethacrylate, a poly(ethyleneglycol)urethane diacrylate, a poly(ethyleneglycol)urethane dimethacrylate, a polyester diacrylate, a polyester dimethacrylate, a poly(ethyleneglycol)urethane triacrylate, a poly(ethyleneglycol)urethane trimethacrylate, a trimethylolpropane triacrylate, a trimethylolpropane trimethacrylate, an ethoxy-substituted trimethylolpropane triacrylate, a propoxy-substituted trimethylolpropane triacrylate, glyceryl triacrylate, glyceryl trimethacrylate, tetramethylolpropane tetraacrylate, di(trimethylolpropane)tetraacrylate, or a combination thereof.
24. The method of claim 22 , wherein a weight ratio between the metal-organic framework and the (meth)acrylate monomer of the monomer composition is about 1:0.5 to about 1:1.