Battery separator, battery including the separator, and method and system for forming same
View Patent ↗Microporous sheet product suitable for use as a battery separator and method of forming the same. According to one embodiment, the method involves forming an extrusion mixture of one or more thermoplastic polymers and a fluid having a high vapor pressure. Next, the mixture is extruded through a die head, cooled and shaped in a first vapor zone under an above-UEL condition to form a solid sheet material. Next, the sheet material is subjected to a two-step process in a second vapor zone under a below-LEL condition, the first step involving a first stretching/fluid vaporization at a higher temperature, the second step involving a second stretching/fluid vaporization at a lower temperature. The resultant sheet is then annealed, and the remainder of fluid is removed to form a sheet product having a thickness characterized by a structure of smaller and larger pore strata across its thickness.
1. A lithium-based battery cell, the lithium-based battery cell comprising:
(a) an electrolyte, the electrolyte comprising a non-aqueous solvent and a lithium salt, the lithium salt dissolved in the non-aqueous solvent;
(b) an anode, the anode contacting the electrolyte;
(c) a cathode, the cathode contacting the electrolyte;
(d) a battery separator, the battery separator separating the anode and the cathode, wherein the battery separator is a microporous sheet product comprising a first polymer and a second polymer, the first polymer comprising a thermoplastic polymer, the second polymer comprising a condensation polymerization polymer that is produced in a dehydration polymerization reaction and that, when exposed to water, undergoes a reduction in molecular weight, wherein, at completion of cell manufacture, the second polymer has an initial total weight, and wherein the second polymer is selected from the group consisting of polyoxyethylene and polypropylene glycol; and
(e) a housing, wherein the electrolyte, the anode, the cathode, and the battery separator are disposed within the housing;
(f) wherein, at completion of cell manufacture, an initial amount of water having an initial total weight is present within the housing and wherein a ratio of the initial total weight of the second polymer to the initial total weight of water is in a range of about 10:1 to 5,000:1.
2. The lithium-based battery cell as claimed in claim 1 wherein the first polymer comprises at least one polyolefin selected from the group consisting of polyethylene, polypropylene, ethylene-butene copolymers, ethylene-hexene copolymers, and combinations thereof.
3. The lithium-based battery cell as claimed in claim 1 wherein the second polymer has a minimum entanglement molecular weight of at least 1000 Da.
4. The lithium-based battery cell as claimed in claim 1 wherein the microporous sheet product is made by a method comprising (a) melt-extruding an extrusion mixture to form a sheet material, the extrusion mixture comprising (i) the first polymer, (ii) the second polymer and (iii) a compatibilizing agent, the compatibilizing agent promoting mixing of the first and second polymers; and (b) then, cooling the sheet material, whereby micropores are formed in the sheet material.
5. The lithium-based battery cell as claimed in claim 1 wherein, after exposure to water, the second polymer undergoes a reduction in average molecular weight of between 20% and 90%, with a minimum cleavage ratio Rc of at least 1.1, wherein the minimum cleavage ratio is defined as average initial molecular weight of the condensation polymerization polymer divided by average final molecular weight of the condensation polymerization polymer after hydrolysis cleavage.
6. The lithium-based battery cell as claimed in claim 1 wherein the ratio of the initial total weight of the second polymer to the initial total weight of water is at least 50:1 and wherein the lithium-based battery cell initially contains, at completion of cell manufacture, greater than 10 ppm of water.
7. The lithium-based battery cell as claimed in claim 1 wherein the second polymer has an initial average molecular weight of at least 12,000 Da.
8. The lithium-based battery cell as claimed in claim 1 wherein the second polymer has an initial molecular weight of at least 110,000 Da.
9. The lithium-based battery cell as claimed in claim 1 wherein the second polymer and the first polymer have an initial average molecular weight ratio of below 2:1 and above 0.01:1, wherein the second polymer and the first polymer have an initial weight ratio of between 0.01:1 and 1:1, and wherein a ratio of average initial molecular weight of the second polymer to average final molecular weight of the second polymer is at least 1:1 and less than 1000:1.
10. The lithium-based battery cell as claimed in claim 4 wherein the compatibilizing agent comprises at least one organic fluid, wherein the first polymer constitutes about 10 to 60% by weight of the extrusion mixture, the second polymer constitutes about 2.1 to 9.9% by weight of the extrusion mixture, and the compatibilizing agent constitutes about 40 to 75% by weight of the extrusion mixture.
11. The lithium-based battery cell as claimed in claim 1 wherein the moisture in the separator is below 300 ppm and wherein the lithium-based battery cell initially contains, at completion of cell manufacture, greater than 40 ppm of water.
12. The lithium-based battery cell as claimed in claim 1 wherein the first polymer and the second polymer are molecularly interwoven using a total melting energy input of at least 0.15 kwh/kg.
13. The lithium-based battery cell as claimed in claim 1 wherein the ratio of the initial total weight of the second polymer to the initial total weight of water in the range of about 500:1 to 5,000:1.
14. A lithium-based battery cell, the lithium-based battery cell comprising:
(a) an electrolyte, the electrolyte comprising a non-aqueous solvent and a lithium salt, the lithium salt dissolved in the non-aqueous solvent;
(b) an anode, the anode contacting the electrolyte;
(c) a cathode, the cathode contacting the electrolyte;
(d) a battery separator, the battery separator separating the anode and the cathode, wherein the battery separator is a microporous sheet product comprising a first polymer and a second polymer, the first polymer comprising a thermoplastic polymer, the second polymer comprising a condensation polymerization polymer that is produced in a dehydration polymerization reaction and that, when exposed to water, undergoes a reduction in molecular weight, wherein, at completion of cell manufacture, the second polymer has an initial total weight, and wherein the second polymer comprises a homopolymer of polyoxyethylene and a copolymer of polyamide 6/12 and wherein an initial weight ratio of the homopolymer to the copolymer is in a range of 0.1:1 to 10:1; and
(e) a housing, wherein the electrolyte, the anode, the cathode, and the battery separator are disposed within the housing;
(f) wherein, at completion of cell manufacture, an initial amount of water having an initial total weight is present within the housing and wherein a ratio of the initial total weight of the second polymer to the initial total weight of water is in a range of about 10:1 to 5,000:1.
15. A lithium-based battery cell, the lithium-based battery cell comprising:
(a) an electrolyte, the electrolyte comprising a non-aqueous solvent and a lithium salt, the lithium salt dissolved in the non-aqueous solvent;
(b) an anode, the anode contacting the electrolyte;
(c) a cathode, the cathode contacting the electrolyte;
(d) a battery separator, the battery separator separating the anode and the cathode, wherein the battery separator is a microporous sheet product comprising a first polymer and a second polymer, the first polymer comprising a thermoplastic polymer, the second polymer comprising a condensation polymerization polymer that is produced in a dehydration polymerization reaction and that, when exposed to water, undergoes a reduction in molecular weight, wherein, at completion of cell manufacture, the second polymer has an initial total weight, and wherein the microporous sheet product is a multilayered structure comprising a core layer and two outer layers, with each layer of the multilayered structure comprising the thermoplastic polymer and the condensation polymerization polymer, and wherein a ratio of the condensation polymerization polymer to the thermoplastic polymer is at least 1.5 times greater in the core layer than in the outer layers; and
(e) a housing, wherein the electrolyte, the anode, the cathode, and the battery separator are disposed within the housing;
(f) wherein, at completion of cell manufacture, an initial amount of water having an initial total weight is present within the housing and wherein a ratio of the initial total weight of the second polymer to the initial total weight of water is in a range of about 10:1 to 5,000:1.
16. The lithium-based battery cell as claimed in claim 15 wherein the second polymer is at least one member selected from the group consisting of polyamide, polyether, polyester, polyoxyethylene, polyethylene glycol, polypropylene glycol, polycarbonate, polyanhydride, polyimide, polybenzimidazole, polyacetal, polysulfone, polyphenylene oxide, and polyurethane.
17. The lithium-based battery cell as claimed in claim 15 wherein the second polymer comprises at least one of (i) a copolymer, (ii) a terpolymer, and (iii) a mixture of at least two polymers, at least one of the at least two polymers of the mixture being a copolymer, wherein an initial weight ratio of the copolymer of the mixture to the total condensation polymerization polymer is 0.1:1 to 0.9:1.
18. The lithium-based battery cell as claimed in claim 15 wherein the second polymer comprises at least one polyamide and wherein the at least one polyamide is selected from the group consisting of at least one homopolymer, at least one copolymer, at least one terpolymer, and combinations thereof.
19. The lithium-based battery cell as claimed in claim 18 wherein the at least one polyamide has a relative viscosity, as compared to m-Cresol, of at least 1.4:1.