Chemistry: electrical current producing apparatus – product – and – With control means responsive to battery condition sensing... – Temperature control
Reexamination Certificate
1998-03-12
2001-01-30
Kalafut, Stephen (Department: 1745)
Chemistry: electrical current producing apparatus, product, and
With control means responsive to battery condition sensing...
Temperature control
C429S145000
Reexamination Certificate
active
06180280
ABSTRACT:
FIELD OF THE INVENTION
The invention is directed to a trilayer shutdown battery separator, and the method of making same.
BACKGROUND OF THE INVENTION
A battery normally comprises electrodes, electrolyte, and battery separators. Battery separators are located between adjacent anodes and cathodes in a battery to prevent direct contact between electrodes of opposite polarity and to contain electrolyte.
In lithium batteries (e.g., lithium ion or lithium secondary battery) which are increasingly popular, short-circuiting is a problem as it tends to cause thermal runaway and even explosion. Thus, shutdown separators have been developed to cope with this problem. (see, e.g., U.S. Pat.. No. 4,650,730 and U.S. Pat. No. 4,731,304 both issued to Lundquist et al.) A shutdown battery separator is a microporous membrane which closes its pores at some temperature well below the melting and/or ignition point of lithium to minimize the negative impact of thermal runaway.
Microporous membranes made of polymers such as polypropylene which give rise to higher puncture strength often have a high melting temperature, near the melting point of lithium, which is a drawback for using these polymers to form shutdown separators for lithium batteries. On the other hand, microporous membranes made of polymers such as polyethylene have low melting temperatures. But their puncture strength is generally low. Thus, trilayer shutdown batteries have been proposed comprising two microporous polypropylene membranes sandwiching a polyethylene membrane.
Japanese Patent Application No. 98395/1994 (JP7-304110A) filed May 12, 1994 by Ube Industries, Ltd. discloses a microporous trilayer battery separator having a polypropylene-polyethylene-polypropylene construction. The trilayer battery separator has a pore-closing shutdown temperature of 135 to 140° C. The process of preparing the separator includes the steps of: extruding a polypropylene non-porous precursor; extruding a polyethylene non-porous precursor; forming the polypropylene-polyethylene-polypropylene non-porous trilayer precursor; bonding the trilayer precursor together; heat-treating (annealing) the bonded precursor; and stretching the bonded, annealed precursor to form the porous, trilayer separator.
U.S. patent application Ser. No. 359,772 filed Dec. 20, 1994 by Hoechst Celanese Corporation also teaches a trilayer battery separator having a polypropylene-polyethylene-polypropylene construction. The shutdown temperature given in the example is 132° C. The process for making the trilayer battery separator includes the steps of: forming a porous polypropylene precursor; forming a porous polyethylene precursor; forming a porous trilayer precursor; and bonding the porous trilayer precursor to form the trilayer battery separator.
UK Patent publication No. GB 2,298,817 describes a microporous trilayer battery separator made by co-extruding a trilayer film precursor having a non-porous polypropylene-polyethylene-polypropylene construction, annealing the trilayer precursor, and then stretching the annealed trilayer precursor to form the porous trilayer battery separator. The separator has a shutdown temperature of 135° C. as given in the examples.
A porous trilayer separator proposed in Japanese Patent Application No. 56320/1995 (JP8-250097A) filed by Kureha Chemical Industry Co. Ltd., is purported to have a shutdown temperature in the range of from 100° C. to 150° C. However, in the working examples, the shutdown temperature of the trilayer separators is 124° C. The Kureha separator is prepared by a process that includes the steps of: co-extruding a trilayer precursor which contains, e.g., a solvent extractable material as pore forming aid, and forming pores in the precursor by solvent extraction of the precursor.
A microporous shutdown separator should be thin enough to minimize the space it occupies in the battery and to reduce electrolytic resistance. Nevertheless the shutdown separator must also have sufficient strength to resist splitting and puncture. Although these two attributes, i.e., thinness and strength, are each very important, the two cannot be maximized since film strength typically varies inversely with film thickness. Moreover, it is also desirable to provide a separator having a shutdown temperature lower than 120° C., preferably within the range of from about 95° C. to about 115° C., while having a higher temperature at which the integrity of the separator can be maintained. As discussed above, the previously disclosed trilayer shutdown separators all have a shutdown temperature higher than 120° C. This is largely because the methods heretofore known for lowering shutdown temperature either compromise separator thinness or substantially weaken separator strength and interfere with the ability to manufacture the separator. Consequently, there has not been available in the art a trilayer separator having a shutdown temperature of lower than 120° C. while still possessing satisfactory thinness as well as sufficient strength. Thus, there is further need for high quality battery separators.
SUMMARY OF THE INVENTION
The three desirable features, i.e., satisfactory thinness, sufficient strength, and relatively low shutdown temperature, are achieved in the trilayer shutdown battery separator provided in the present invention. The battery separator of this invention has two microporous strength layers sandwiching an inner microporous shutdown layer. The microporous inner layer is formed by a phase inversion method while the strength layers are made by stretch method. Preferably, the thickness of the trilayer separator is no greater than about 2 mils, and more preferably no greater than about 1 mil. Preferably, the trilayer separator has a shutdown temperature of lower than about 124° C., more preferably within the range of from about 80° C. to about 120° C., even more preferably from about 95° C. to about 115° C. Methods of making the trilayer shutdown separator are also provided. A preferred method comprises the following steps: (a) extruding non-porous strength layer precursors; (b) annealing and stretching the non-porous precursor to form microporous strength layers; (c) forming a microporous inner layer by a phase inversion process which comprises extruding a non-porous shutdown layer precursor from a composition comprising a polymer and extractable materials, extracting the extractable materials from the precursor to form a microporous structure, and optionally, stretching the membrane to orient the microporous membrane; and (d) bonding the precursors into a trilayer battery separator wherein the first and third layers are strength layers, and the second layer is said microporous membrane made by a phase inversion method.
The trilayer battery separator provided in this invention has sufficient strength and low shutdown temperature while its thinness is not sacrificed. Thus, it is particularly suitable for use in batteries, such as lithium secondary batteries.
REFERENCES:
patent: 4247498 (1981-01-01), Castro
patent: 4539256 (1985-09-01), Shipman
patent: 4650730 (1987-03-01), Lundquist et al.
patent: 4731304 (1988-03-01), Lundquist et al.
patent: 5281491 (1994-01-01), Rein et al.
patent: 5565281 (1996-10-01), Yu et al.
patent: 5691047 (1997-11-01), Kurauchi et al.
patent: 5691077 (1997-11-01), Yu
patent: 2 298 817 (1996-09-01), None
patent: 7-307146 (1995-11-01), None
patent: 96250097 (1996-09-01), None
U.S. application Ser. No. 08/896,513, filed Jun. 22, 1997 entitledUltra-thin, Single-ply Battery Separator;Inventor: Wei-Ching Yu; application consisting of 27 pages and 2 sheets of drawings.
U.S. Continuation application Ser. No. 08/650,210; filed May 20, 1996 entitledShutdown, Trilayer Battery Separator;Inventor: Wei-Ching Yu; application consisting of 27 pgs. and 2 sheets of drawings.
Celgard Inc.
Hammer III Robert H.
Kalafut Stephen
Wills M.
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