Lithium cationic single-ion conducting filler-containing composite polymer electrolyte for lithium secondary battery and method of manufacturing the same

Abstract

Provided are a composite polymer electrolyte for a lithium secondary battery in which a composite polymer matrix multi-layer structure composed of a plurality of polymer matrices with different pore sizes is impregnated with an electrolyte solution, and a method of manufacturing the same. Among the polymer matrices, a microporous polymer matrix with a smaller pore size contains a lithium cationic single-ion conducting inorganic filler, thereby enhancing ionic conductivity, the distribution uniformity of the impregnated electrolyte solution, and maintenance characteristics. The microporous polymer matrix containing the lithium cationic single-ion conducting inorganic filler is coated on a surface of a porous polymer matrix to form the composite polymer matrix multi-layer structure, which is then impregnated with the electrolyte solution, to manufacture the composite polymer electrolyte. The composite polymer electrolyte is used in a unit battery. The composite polymer matrix structure can increase mechanical properties. The introduction of the lithium cationic single-ion conducting inorganic filler can provide excellent ionic conductivity and high rate discharge characteristics.

What is claimed is: 
     
       1. A composite polymer electrolyte for a lithium secondary batterycomprising:
 a first polymer matrix made of a first porous polymer with a first pore size; 
 a second polymer matrix comprising a second porous polymer with a second pore size smaller than the first pore size and a lithium cationic single-ion conducting inorganic filler, the lithium cationic single-ion conducting inorganic filler comprises an inorganic filler particle and an ionic hydrophilic group containing a Li cationic single ion introduced onto a surface of the inorganic filler particle; and 
 an electrolyte solution impregnated into the first polymer matrix and the second polymer matrix. 
 
     
     
       2. The composite polymer electrolyte of  claim 1 , wherein the inorganic filler particle is selected from the group consisting of silica, talc, alumina (Al 2 O 3 ), y -LiAIO 2 , Ti0 2 , zeolite, molybdenum phosphate hydrate, and tungsten phosphate hydrate. 
     
     
       3. The composite polymer electrolyte of  claim 1 , wherein an introduction ratio of the ionic hydrophilic group on the surface of the inorganic filler particle is 0.001 to 99.999wt %. 
     
     
       4. The composite polymer electrolyte of  claim 1 , wherein the ionic hydrophilic group is a single- or a multiple-species functional group selected from SO 3 Li + , SO2C 6 H 4 COO − Li + , C 6 H 3 (SO 2 NH 2 )COO − Li + , CH(COO − Li)CH 2 COO − Li+ CH(COO − Li)CH 2 COO − Li + , C 6 H 3 (OH)COO − Li + , C 6 H 3 (OH)COO − Li + , C 6 H 2 (NO 2 ) 2 COO − Li+ C 6 H 2 (NO 2 ) 2 COO − Li + , CH 2 C(CH 3 ) 2 COO − Li + , Si(CH 3 ) 2 (CH 2 )xC(CF 3 ) 2 (CF 2 )ySO 3   − Li + , Si(CH 3 ) 2 (CH 2 )xC(CF 3 ) 2 (CF 2 )yCOO 31 Li   + , Si(CH 2 )xC(CF 3 ) 2 (CF 2 )ySO 3   − Li + , Si(CH 2 )xC(CF 3 ) 2 (CF 2 )yCOO − Li + , Si(CF 3 ) 2 (CF 2 )ySO 3   − Li + , Si(CF3)2(CF2)yCOO−Li+ Si(CF 3 ) 2 (CF 2 )yCOO − Li + , Si(CF2)ySO3−Li+Si(CF 2 )ySO 3− Li + , and Si(CF2)y COO −L1+ Si(CF 2 )y COO  − L1 + , where X and Y are each independently an integer of 0 to 10. 
     
     
       5. The composite polymer electrolyte of  claim 1 , wherein the lithium cationic single-ion conducting inorganic filler further comprises a hydrophobic group introduced onto the surface of the inorganic filler particle. 
     
     
       6. The composite polymer electrolyte of  claim 5 , wherein the hydrophobic group is a single- or multiple-species group selected from (CH 2 ) 3 CH 3 , (CH 2 ) 5 CH 3 , (CH 2 ) 6 CH 3 , Si(CH 3 ) 2 C 2 H 5 , CF 2 CH 3 , C 2 H 5 , Si(C 2 H 5 ) 3 , Si(CH 3 ) 3 , Si(CH 3 ) 2 C(CH 3 ) 2 CH(CH 3 ) 2 , SCN(CH 3 ) 2 , Si(C 6 H 5 ) 2 CH 3 , Si(CH 3 ) 2 C 6 H 5 , SiH(CH 3 ) 2 , and Si(CH 3 ) 2 CH═CH 2 . 
     
     
       7. The composite polymer electrolyte of  claim 1 , wherein the first porous polymer is polyethylene, polypropylene, polyimide, polysulfone, polyurethane, polyvinylchioride, cellulose, nylon, polyacrylonitrile, polyvinylidene fluoride, polytetrafluoroethylene, a copolymer or blend thereof. 
     
     
       8. The composite polymer electrolyte of  claim 1 , wherein the second porous polymer is a vinylidene fluoride based polymer, an acrylate based polymer, a copolymer or blend thereof. 
     
     
       9. The composite polymer electrolyte of  claim 8 , wherein the second porous polymer is a copolymer of vinylidene fluoride and hexafluoropropylene, a copolymer of vinylidene fluoride and trifluoroethylene, a copolymer of vinylidene fluoride and tetrafluoroethylene, polymethylacrylate, polyethylacrylate, polymethylmethacrylate, polyethylmethacrylate, polybutylacrylate, polybutylmethacrylate, polyvinylacetate, polyethylene oxide, polypropylene oxide, a copolymer or blend thereof. 
     
     
       10. The composite polymer electrolyte of  claim 1 , wherein the lithium cationic single-ion conducting inorganic filler is added in an amount of 1 to 100 wt %, based on the total weight of polymers constituting the second polymer matrix. 
     
     
       11. The composite polymer electrolyte of  claim 1 , wherein the first polymer matrix has a thickness of 1 to 25 μm and the second polymer matrix has a thickness of 0.1 to 15 μm. 
     
     
       12. The composite polymer electrolyte of  claim 1 , wherein the electrolyte solution is made of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methylethyl carbonate, tetrahydrofuran, 2-methyltetrahydrofuran, dimethoxyethane, methyl formate, ethyl formate, gamma-butyrolactone, or a mixture thereof. 
     
     
       13. The composite polymer electrolyte of  claim 1 , wherein the electrolyte solution is impregnated into the first polymer matrix and the second polymer matrix in an amount of 1 to 1,000 wt %, based on the total weight of polymers constituting the first polymer matrix and the second polymer matrix. 
     
     
       14. The composite polymer electrolyte of  claim 1 , wherein the electrolyte solution comprises at least one lithium salt selected from the group consisting of lithium perchlorate (LiCIO 4 ), lithium triflate (LiCF 3 SO 3 ), lithium hexafluorophosphate (LiPF 6 ), and lithium tetrafluoroborate (LiBF 4 ), and lithium trifluoromethanesulfonylimide (LiN(CF 3 SO 2 ) 2 ). 
     
     
       15. The composite polymer electrolyte of  claim 14 , wherein the lithium salt is dissolved in the electrolyte solutionin an amount of 1 to 200 wt %, based on the total weight of polymers constituting the first polymer matrix and the second polymer matrix. 
     
     
       16. A method of manufacturing a composite polymer electrolyte for a lithium secondary battery, the method comprising:
 forming a first polymer matrix made of a first porous polymer with a first pore size; 
 synthesizing a lithium cationic single-ion conducting inorganic filler using an inorganic filler particle as a starting material, the lithium cationic single-ion conducting inorganic filler comprises an inorganic filler particle and an ionic hydrophilic group containing a Li cationic single ion introduced onto a surface of the inorganic filler particle and wherein synthesizing the lithium cationic single-ion conducting inorganic filler comprises substituting a surface hydroxyl group (—OH) of the inorganic filler particle by a functional group containing a sulfonic acid group (—SO 3 H) or a carboxyl group (—COOH); and substituting a proton (H 30 ) of the sulfonic acid group (—SO 3 H) or carboxyl group (—COOH) by a lithium ion (Li+) (Li + ); 
 dissolving a second porous polymer with a second pore size smaller than the first pore size and the lithium cationic single-ion conducting inorganic filler in a co-solvent to prepare a mixed solution; 
 coating the first polymer matrix with the mixed solution to form a second polymer matrix on the first polymer matrix; and 
 impregnating the first polymer matrix and the second polymer matrix with an electrolyte solution. 
 
     
     
       17. The method of  claim 16 , wherein the co-solvent is selected from the group consisting of acetone, dimethylformamide, dimethylsufoxide, N-methylpyrrolidone, and a mixture thereof. 
     
     
       18. A method of manufacturing a composite polymer electrolyte for a lithium secondary battery, the method comprising:
 forming a first polymer matrix made of a first porous polymer with a first pore size;   synthesizing a lithium cationic single-ion conducting inorganic filler, the lithium cationic single-ion conducting inorganic filler comprising an inorganic filler particle and an ionic hydrophilic group containing a Li cationic single ion introduced onto a surface of the inorganic filler particle;   dissolving a second porous polymer with a second pore size and the lithium cationic single-ion conducting inorganic filler in a co-solvent to prepare a mixed solution;   coating the first polymer matrix with the mixed solution to form a second polymer matrix; and   impregnating the first polymer matrix and the second polymer matrix with an electrolyte solution.   
     
     
       19. A method of manufacturing a composite polymer electrolyte for a lithium secondary battery, the method comprising:
 forming a first polymer matrix made of a first porous polymer with a first pore size;   synthesizing a lithium cationic single-ion conducting inorganic filler comprising an inorganic filler particle, wherein synthesizing the lithium cationic single-ion conducting inorganic filler comprises substituting a surface hydroxyl group (—OH) of the inorganic filler particle by at least one of an ionic hydrophilic group and a hydrophobic group;   dissolving a second porous polymer with a second pore size smaller than the first pore size and the lithium cationic single-ion conducting inorganic filler in a co-solvent to prepare a mixed solution;   coating the first polymer matrix with the mixed solution to form a second polymer matrix; and   impregnating the first polymer matrix and the second polymer matrix with an electrolyte solution.   
     
     
       20. The method of claim 19, wherein the synthesizing the lithium cationic single-ion conducting inorganic filler further comprises:
 substituting the surface hydroxyl group (—OH) of the inorganic filler particle by a function group containing a sulfonic acid group (—SO 3 H) or a carboxyl group (—COOH); and   substituting a proton (H 30  ) of the sulfonic acid group (—SO 3 H) or carboxyl group (—COOH) by a lithium ion (Li + ).