Separator for a high energy rechargeable lithium battery

Abstract

The instant invention is directed to a separator for a high energy rechargeable lithium battery and the corresponding battery. The separator includes a ceramic composite layer and a polymeric microporous layer. The ceramic layers includes a mixture of inorganic particles and a matrix material. The ceramic layer is adapted, at least, to block dendrite growth and to prevent electronic shorting. The polymeric layer is adapted, at least, to block ionic flow between the anode and the cathode in the event of thermal runaway.

What is claimed is: 
     
       1. A separator for a high energy rechargeable lithium battery comprises:
 at least one ceramic composite layer, said layer including a mixture of inorganic particles in a matrix material; said layer being adapted to at least block dendrite growth and to prevent electronic shorting; and   at least one polyolefinic microporous layer, said layer being adapted to block ionic flow between an anode and a cathode.   
     
     
       2. The separator according to  claim 1  wherein said mixture comprises between 20% to 95% by weight of said inorganic particles and between 5% to 80% by weight of said matrix material. 
     
     
       3. The separator according to  claim 1  wherein said inorganic particles are selected from the group consisting of SiO 2 , Al 2 O 3 , CaCO 3 , TiO 2 , SiS 2 , SiPO 4 , and mixtures thereof. 
     
     
       4. The separator according to  claim 1  wherein said matrix material is selected from the group consisting of polyethylene oxide, polyvinylidene fluoride, polytetrafluoroethylene, polyurethane, polyacrylonitrile, polymethylmethacrulate, polytetraethylene glycol diacrylate, copolymers thereof, and mixtures thereof. 
     
     
       5. The separator according to  claim 1  wherein said polyolefinic microporous layer is a polyolefinic membrane. 
     
     
       6. The separator according to  claim 5  wherein said polyolefinic membrane is a polyethylene membrane. 
     
     
       7. A separator for a high energy rechargeable lithium battery comprises:
 at least one ceramic composite layer or coating, said layer including a mixture of 20-95% by weight of inorganic particles selected from the group consisting of SiO 2 , Al 2 O 3 , CaCO 3 , TiO 2 , SiS 2 , SiPO 4 , and mixtures thereof, and 5-80% by weight of a matrix material selected from the group consisting of polyethylene oxide, polyvinylidene fluoride, polytetrafluoroethylene, copolymers of the foregoing, and mixtures thereof; and   at least one polyolefinic microporous layer having a porosity in the range of 20-80%, an average pore size in the range of 0.02 to 2 microns, and a Gurley Number in the range of 15 to 150 sec.   
     
     
       8. The separator according to  claim 7  wherein said inorganic particles have an average particle size in the range of 0.001 to 24 microns. 
     
     
       9. The separator according to  claim 7  wherein said inorganix particles are selected from the group consisting of SiO 2 , Al 2 O 3 , CaCO 3 , and mixtures thereof. 
     
     
       10. The separator according to  claim 7  wherein said matrix material is selected from the group consisting of polyvinylidene fluoride and/or polyethylene oxide, their copolymers, and mixtures thereof. 
     
     
       11. A high energy rechargeable lithium battery comprising:
 an anode containing lithium metal or lithium-alloy or a mixtures of lithium metal and/or lithium alloy and another material;   a cathode;   a separator according to  claims 1 - 10  disposed between said anode and said cathode; and   an electrolyte in ionic communication with said anode and said cathode via said separator.   
     
     
       12. A separator for an energy storage system comprises:
 at least one ceramic composite layer or coating, said layer including a mixture of 20-95% by weight of inorganic particles selected from the group consisting of SiO 2 , Al 2 O 3 , CaCO 3 , TiO 2 , SiS 2 , SiPO 4 , [and the like] and mixtures thereof, and 5-80% by weight of a matrix material selected from the group consisting of polyethylene oxide, polyvinylidene fluoride, polytetrafluoroethylene, copolymers of the foregoing, and mixtures thereof, said layer being adapted to at least block dendrite growth and to prevent electronic shorting; and 
 at least one polyolefinic microporous layer having a porosity in the range of 20-80%, an average pore size in the range of 0.02 to 2 microns, and a Gurley Number in the range of 15 to 150 sec, said layer being adapted to block ionic flow between an anode and a cathode. 
 
     
     
       13. A separator for a rechargeable lithium battery comprising:
 at least one ceramic composite layer wherein the ceramic composite layer includes a mixture of inorganic particles in a matrix material and wherein the ceramic composite layer is adapted to at least block dendrite growth after repetitive charge-discharge cycling and to prevent electronic shorting, wherein the ceramic composite layer is nonporous such that pores are formed once in contact with an electrolyte; and   at least one polyolefinic microporous layer wherein the layer is adapted to block ionic flow between an anode and a cathode.   
     
     
       14. The separator according to claim 13 wherein the ceramic composite layer is a coating. 
     
     
       15. The separator according to claim 14 wherein the coating thickness is in the range of about 0.01 to 25 microns. 
     
     
       16. The separator according to claim 13 wherein the matrix material comprises polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyurethane, polyacrylonitrile (PAN), polymethylmethacrylate (PMMA), polytetraethylene glycol diacrylate, copolymers thereof, or mixtures thereof. 
     
     
       17. The separator according to claim 16 wherein the matrix material comprises polyvinylidene fluoride (PVDF), polyethylene oxide (PEO), copolymers thereof, or mixtures thereof. 
     
     
       18. The separator according to claim 13 wherein the matrix material comprises a gel forming polymer. 
     
     
       19. The separator according to claim 13 wherein the matrix material is a continuous material in which the inorganic particles are embedded. 
     
     
       20. The separator according to claim 13 wherein the inorganic particles have an average particle size in the range of 0.001 to 24 microns. 
     
     
       21. The separator according to claim 13 wherein the inorganic particles comprise silicon dioxide (SiO 2 ), aluminum oxide (Al 2 O 3 ), calcium carbonate (CaCO 3 ), titanium dioxide (TiO 2 ), SiS 2 , SiPO 4 , or mixtures thereof. 
     
     
       22. The separator according to claim 13 wherein the inorganic particles comprise silicon dioxide (SiO 2 ), aluminum oxide (Al 2 O 3 ), calcium carbonate (CaCO 3 ), or mixtures thereof. 
     
     
       23. The separator according to claim 13 wherein the polyolefinic microporous layer comprises polyethylene or polypropylene. 
     
     
       24. The separator according to claim 13 wherein the polyolefinic microporous layer is a polyolefinic membrane. 
     
     
       25. The separator according to claim 24 wherein the polyolefinic membrane is a polyethylene membrane. 
     
     
       26. The separator according to claim 13 wherein the ceramic composite layer prevents electronic shorting by eliminating soft shorts caused by dendrites. 
     
     
       27. The separator according to claim 13 wherein the ceramic composite layer prevents electronic shorting by eliminating soft shorts caused by dendrites that grow during repetitive charge-discharge cycling. 
     
     
       28. A separator for a rechargeable lithium battery comprising:
 at least one ceramic composite layer, wherein the ceramic composite layer comprises:
 a mixture of about 20-95% by weight of inorganic particles, and 
 about 5-80% by weight of a matrix material, 
 wherein the ceramic composite layer is adapted to at least block dendrite growth after repetitive charge-discharge cycling and thereby to prevent electronic shorting and the ceramic composite layer is nonporous such that pores are formed once in contact with an electrolyte; and 
   at least one polyolefinic microporous layer having a porosity in the range of about 20-80%, an average pore size in the range of about 0.02 to 2 microns, and wherein the polyolefinic microporous layer is adapted to block ionic flow between an anode and a cathode.   
     
     
       29. The separator according to claim 28 wherein the ceramic composite layer is a coating. 
     
     
       30. The separator according to claim 29 wherein the coating thickness is in the range of about 0.01 to 25 microns. 
     
     
       31. The separator according to claim 28 wherein the matrix material comprises polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyurethane, polyacrylonitrile (PAN), polymethylmethacrylate (PMMA), polytetraethylene glycol diacrylate, copolymers thereof, or mixtures thereof. 
     
     
       32. The separator according to claim 31 wherein the matrix material comprises polyvinylidene fluoride (PVDF), polyethylene oxide (PEO), copolymers thereof, or mixtures thereof. 
     
     
       33. The separator according to claim 28 wherein the matrix material comprises a gel forming polymer. 
     
     
       34. The separator according to claim 28 wherein the matrix material is a continuous material in which the inorganic particles are embedded. 
     
     
       35. The separator according to claim 28 wherein the inorganic particles have an average particle size in the range of about 0.001 to 24 microns. 
     
     
       36. The separator according to claim 28 wherein the inorganic particles comprise silicon dioxide (SiO 2 ), aluminum oxide (Al 2 O 3 ), calcium carbonate (CaCO 3 ), titanium dioxide (TiO 2 ), SiS 2 , SiPO 4 , or mixtures thereof. 
     
     
       37. The separator according to claim 36 wherein the inorganic particles comprise silicon dioxide (SiO 2 ), aluminum oxide (Al 2 O 3 ), calcium carbonate (CaCO 3 ), or mixtures thereof. 
     
     
       38. The separator according to claim 28 wherein the ceramic composite layer prevents electronic shorting by eliminating soft shorts caused by dendrites. 
     
     
       39. The separator according to claim 28 wherein the ceramic composite layer prevents electronic shorting by eliminating soft shorts caused by dendrites that grow during repetitive charge-discharge cycling.