Chemistry: electrical current producing apparatus – product – and – Current producing cell – elements – subcombinations and... – Include electrolyte chemically specified and method
Reexamination Certificate
2001-11-28
2004-11-02
Tsang-Foster, Susy (Department: 1745)
Chemistry: electrical current producing apparatus, product, and
Current producing cell, elements, subcombinations and...
Include electrolyte chemically specified and method
C429S248000, C429S249000, C429S250000
Reexamination Certificate
active
06811927
ABSTRACT:
TECHNICAL FIELD
The present invention relates to a battery containing built-in polycarbodiimide. According to the invention, battery self-discharge is inhibited and the battery life is prolonged.
BACKGROUND ART
Secondary batteries such as nickel-hydrogen cells and nickel-cadmium (Ni—Cd) cells are recently expected to be used as power sources for electric cars as well as small batteries for electrical/electronic appliances. Such a secondary battery is generally constituted of a positive electrode, a negative electrode, and a separator. Among these, the separator serves to prevent the cell from short-circuiting between the electrodes and enable ions to pass therethrough, and is required to have hydrophilicity, chemical resistance, and mechanical strength. Conventionally known as a separator is a hydrophilic nonwoven fabric formed from a polyamide resin or the like. However, this separator has insufficient resistance to chemicals (alkalis and acids). Because of this, separators comprising polyolefin nonwoven fabrics which have undergone various treatments are also known. Specifically, separators obtained by subjecting a polyolefin-based nonwoven fabric to a hydrophilizing treatment, e.g., impregnation with a surfactant, plasma treatment, grafting treatment, sulfonation treatment, or the like, have been proposed (Unexamined Published Japanese Patent Applications Nos. 4-167355 and 11-238496, etc.).
Furthermore, since the polyamide-based nonwoven fabric has amide bonds, batteries employing this as a separator show a higher degree of self-discharge than batteries employing an electrochemically inert polyolefin nonwoven fabric and have poor battery properties. In contrast, batteries employing a separator obtained by subjecting a polyolefin-based nonwoven fabric to a specific treatment cannot be regarded as fully satisfactory in self-discharge characteristics, although superior in overall battery properties to batteries employing the polyamide-based separator.
Specifically, the separator obtained by treating a polyolefin-based nonwoven fabric with a surfactant shows effective hydrophilicity in the initial stage of use. However, when this separator is once immersed in water, taken out therefrom, dried, and reimmersed in water, then the hydrophilicity decreases considerably. In addition, this separator is unsatisfactory in self-discharge characteristics.
Furthermore, the polyolefin-based nonwoven fabric which has undergone a plasma treatment has hydrophilic groups bonded to the substrate surface by covalent bonding and hence retains sufficient wettability even when it is immersed in water, dried once, and reimmersed in water. Namely, it is wet-dry reversible. However, in the case where this nonwoven fabric is immersed in an aqueous alkali solution having a high concentration, it is not wetted by water when it is washed with water, dried, and reimmersed in water. It is presumed that the hydrophilic but weakly adherent, interfacial layer formed on the substrate surface by the plasma treatment was peeled off upon contact with the high-concentration aqueous alkali solution. This separator also is ineffective in greatly improving the inhibition of self-discharge.
In the case of the polyolefin-based nonwoven fabric which has under gone a grafting treatment, a water-soluble monomer is tenaciously bonded to a substrate by covalent bonding. However, the polyolefin treated by grafting with acrylic acid or methacrylic acid has the possibility of undergoing oxidative decomposition in a strongly oxidizing atmosphere because this polyolefins of the carboxylic acid type. Consequently, this nonwoven fabric is used as a battery separator in limited applications.
Furthermore, the polyolefin-based nonwoven fabric which has undergone a sulfonation treatment has sulfo groups tenaciously bonded to the substrate by covalent bonding. Consequently, this nonwoven fabric retains long-lasting hydrophilicity and functions to inhibit a battery from suffering self-discharge. However, the treatment necessitates a post-washing step.
An object of the invention is to provide a battery which is sufficiently inhibited from suffering self-discharge and has excellent battery properties. The present inventors made extensive investigations on the self-discharge of batteries. As a result, it has unexpectedly been found that the self-discharge of a battery is considerably inhibited by causing polycarbodiimide to be present in the battery. The invention has thus been completed.
DISCLOSURE OF THE INVENTION
The invention provides a battery containing a built-in polymer which has in the molecule a carbodiimide unit represented by the following formula (I):
—[—R—N═C═N—]
n
— (I)
(wherein R means an organic group and n means an integer of 1 to 10,000).
The battery of the invention can be inhibited from suffering self-discharge due to the built-in polycarbodiimide represented by general formula (I), which is disposed in any of various forms such as sheet, powder, and particles in or on an electrode or the separator or in other inner part of the battery.
The built-in polycarbodiimide may be disposed in any desired position within the battery. Furthermore, the battery is not particularly limited in steps for the production thereof. In the case where the polycarbodiimide is particulate or powdery, it may be placed in a bag made of a net or porous material having an opening diameter smaller than the particles, so as to prevent the polycarbodiimide from scattering. In the case where the polycarbodiimide is particulate or powdery, it may be present on the surface of or in an inner part of a porous separator substrate. It may have been deposited on the surface of the separator by coating. The polycarbodiimide maybe present on the surface of or in an inner part of an electrode. It may also be present between the separator and an electrode. Incidentally, the polycarbodiimide may be crosslinked if desired.
REFERENCES:
patent: 4190707 (1980-02-01), Doi et al.
patent: 4832869 (1989-05-01), Cotts
patent: 5093214 (1992-03-01), Saito et al.
patent: 6077628 (2000-06-01), Takechi et al.
patent: 2-98004 (1990-04-01), None
patent: 4-167355 (1992-06-01), None
patent: 6-16907 (1994-01-01), None
patent: 10-294129 (1998-11-01), None
patent: 11-238496 (1999-08-01), None
McElhill et al. “New Organic Depolarizers”, Proc. Ann. Power Sources Conf. (1963), 17, pp. 145-148.*
Derwent Abstract for JP 02-098004 A (Apr.1990).*
JPO Machine Translation for JP 06-016907 A (Jan. 1994).*
JPO Machine Translation for JP 08-055620 A (Feb. 1996).*
Derwent abstract for DD 228398 A.*
International Search Report for PCT/JP01/02917 dated Jul. 3, 2001.
Wiff, et al. “Polycarbodiimide and polyimide/cyanate thermoset in situ molecules composites”, Journal of Materials Research, Jul. 1998, vol. 13, No. 7, p. 1840-1847.
Abe Masao
Asai Fumiteru
Kii Keisuke
Kishii Yutaka
Misumi Sadahito
Nitto Denko Corporation
Tsang-Foster Susy
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