JP2002500416A - Battery separator - Google Patents

Abstract

SUMMARY A separator (16) for a battery that does not include a layer of coating material is provided. This separator (16) comprises two layers (16a, 16b) arranged adjacent to each other. These layers may be formed of the same material or different materials. The material may be woven or non-woven. In some embodiments, these layers are formed of the same nonwoven non-membrane material that is a matrix of polyvinyl alcohol fibers, cellulose fibers, and polyvinyl alcohol fibers.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[Industrial applications]

 The present invention relates to batteries.

[0002]

[Prior art]

For example, batteries such as alkaline batteries are usually used as energy sources. Generally, an alkaline battery has a cathode, an anode, a separator, and an electrolyte. The cathode is usually formed of manganese dioxide, carbon particles and a binder. The anode can be formed by a gel containing zinc particles. The separator is usually located between the cathode and the anode. The electrolyte dispersed throughout the battery may be a hydroxide solution.

The present invention relates to a battery having a porous cathode and a porous anode, such as an alkaline battery. These cells have good performance characteristics. For example, high energy can be output at a high discharge rate, which is at least equal to the battery capacity (in amps per hour) per hour. The battery can have various industry standard sizes, for example, AA, AAA, AAAA, C or D.

[0004] "Membrane materials" have an average core diameter of at most 0.5 microns, whereas "non-membrane materials" have at least 5 microns. Of the average core diameter.

[0005]

Summary of the Invention

In one aspect, the invention features a first and second non-woven non-membrane material. The first non-woven non-membrane material does not include any filler,
The second non-woven non-membrane material is disposed along a surface of the first non-woven non-membrane material. This battery separator does not include a membrane material.

[0006] In another aspect, the invention features an electrochemical cell having a major axis and at least one minor axis orthogonal to the major axis. The electrochemical cell includes an anode, a cathode, and a separator disposed between the cathode and the anode. The separator comprises first and second non-woven non-membrane materials. The second nonwoven non-membrane material is provided along a surface of the first nonwoven non-membrane material. At least about 6 in the fiber length direction of the first nonwoven non-membrane material
The 0% length lies within an angle of approximately 10 degrees with respect to a direction parallel to the long axis of the electrochemical cell.

[0007] The fiber length direction of the nonwoven material coincides with an axis along the direction in which the nonwoven material normally faces. However, it should be noted that the individual fibers of these nonwoven materials can be oriented in any direction.

[0008] The first and second nonwoven non-membrane materials can absorb approximately the same amount of electrolyte. For example, the first nonwoven non-membrane material can absorb about 1.1 to about 0.9 times the amount of electrolyte that the second nonwoven non-membrane material can absorb.

[0009] The cathode may include non-synthetic non-expandable graphite particles having an average particle size of less than approximately 20 microns, as measured using a Sympatec HELIOS analyzer. For a given sample of graphite particles, the average particle size is the particle size such that half of the sample volume has a smaller particle size.

“Non-synthetic graphite particles” refers to graphite particles that have been prepared without using an industrial or laboratory graphitization process.

“Non-expandable graphite particles” refers to graphite particles that do not undergo an industrial or laboratory expansion process.

The battery may have a relatively small amount of manganese dioxide and / or zinc particles compared to the amount of electrolyte. For example, the weight distribution ratio of manganese dioxide to electrolyte may be from about 2.2 to about 2.9, and the weight distribution ratio of zinc particles to electrolyte may be from about 0.9 to about 1.25. This weight distribution ratio is
The calculation is based on the amount of electrolyte dispersed throughout the battery.

The cathode may have a porosity of about 21% to about 28%. This cathode porosity depends on the amount of cathode that cannot be increased by solid materials such as manganese dioxide, carbon particles and binders.

The anode has a porosity of about 2 grams to about 2.45 grams of zinc per cubic centimeter of the anode volume increased by the liquid or solid material.

[0015] These batteries have been tested according to the cc photo test, 1 watt continuous test, 1/2 watt continuous test, pulse wave test, 1/2 watt rm test and / or 1/4 watt rm test. AA or A that demonstrates good results
It may be an AA battery. These tests will be described later.

[0016] Other features and advantages of the invention will be apparent from the detailed description of preferred embodiments of the invention, and from the claims.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION

A battery according to a preferred embodiment is an alkaline battery having a separator that does not include a layer of membrane material. FIG. 1 shows a battery 10 having a cathode 12, an anode 14, a separator 16, an outer wall 18 contacting the outside diameter of the cathode 12, and an insulating layer 26. The battery 10 further includes an anode collector 20 that penetrates the seal member 22 and is inserted into the anode 14. The upper end of the anode collector 20 is connected to a negative electrode end cap 24 serving as an external negative electrode of the battery 10. The insulating layer 26 may be formed from an electrically non-conductive material, for example, a heat-shrinkable plastic. Further, the electrolyte is the cathode 12,
It is dispersed throughout the anode 14 and the separator 16.

As shown in FIG. 2, the separator 16 includes a coating material layer 16 a and this layer 16 a.
a), and a coating layer 16b arranged along the surface of FIG. These layers 16a
And 16b may be a single sheet of material folded on itself and wrapped around itself. In other embodiments, layer 16a may be formed of the same or different material as layer 16b. In some embodiments, layer 16a can absorb approximately the same amount of electrolyte as layer 16b absorbs. In these embodiments, layer 16a can absorb about 1.1 to about 0.9 times the amount of electrolyte that layer 16b can absorb. Specifically, layer 16a can absorb about 1.05 to about 0.95 times the amount of electrolyte that layer 16b can absorb.

Materials suitable for use in forming layers 16a and 16b may include any of the conventional non-membrane materials used for separators. Generally, these materials are free of fillers, such as, for example, inorganic particles.

In some embodiments, layer 16a and / or layer 16b can be formed from a woven material. Such materials can be formed, for example, from cellulose, polyvinyl alcohol (PVA), polyamide, polysulfone, and mixtures thereof.

In certain embodiments, layers 16a and 16b each comprise about 20 to about 40 weight percent rayon, about 55 to about 65 weight percent PVA, and about 5 to about 15 weight percent. And a non-woven layer formed of a PVA binder. In one embodiment, layers 16a and 16b each have approximately 57
A nonwoven layer formed by weight percent PVA fibers, approximately 30 weight percent cellulosic fibers, and approximately 13 weight percent PVA binder.

If the separator 16 is too thin, the distance between the cathode 12 and the anode 14 may be shortened. However, separator 16 should not be too thin, as the capacity of battery 10, which can be used as an electrolyte to reduce the energy capacity of cathode 12, anode 14, and battery 10, can be reduced. Therefore, when dry, each of layers 16a and 16b is preferably at least about 4 mm thick, more preferably about 4 mm to about 6 mm thick, and most preferably about 5.4 mm. Millimeter thickness is good. When wet, each of layers 16a and 16b is preferably at least about 8 mm thick, more preferably about 8 mm to about 12 mm thick, and most preferably about 10 mm thick. Good thickness.

The reference weight of the separator 16 should not be too light because the distance between the cathode 12 and the anode 14 cannot be shortened, but if the reference weight of the separator 16 is too heavy, the battery 10 Will have a smaller discharge capacity. Thus, layers 16a and 16b each preferably have at least one
It is formed at a basis weight of 20 grams per square meter, more preferably at about 40 grams to about 60 grams per square meter, and most preferably at 54 grams per square meter.

[0024] Separator 16 may be positioned within battery 10 using any of the conventional processes. Preferably, it is positioned within battery 10 using a cross-positioning technique. In this method, the cathode 12 is formed in the battery 10 and prior to forming the anode 14, the layer 16b is oriented such that its fiber length direction is substantially orthogonal to the fiber length direction of the layer 16a. Is formed on the surface of the layer 16a. The layers 16a and 16b are then pushed into the battery 10 such that a portion of the surface of layer 16a is located along the inner circumference of cathode 12.

In a nonwoven material, the individual fibers can usually be oriented in any direction.
However, as shown in FIG. 3, during the manufacturing process, some non-woven materials may be manufactured in a common orientation along one axis with reference to the length of the fibers therein. good. Layers 16a and 16b are formed of a non-woven material and a cross-over technique is used, preferably at least about 60 of layers 16a and 16b.
% Is in a direction parallel to the longest long axis of the battery 10 within an angle of 10 degrees, and more preferably at least about 8% of the layers 16a and 16b.
5% is the direction parallel to the longest longitudinal axis of the battery 10 within an angle of 10 degrees, and most preferably at least about 9% of the layers 16a and 16b.
0% is a direction in which the angle is parallel to the longest long axis of the battery 10 within a range of 10 degrees.

Cathode 12 may be formed of any of the standard materials used for battery cathodes. Typically, cathode 12 is formed from manganese dioxide, carbon particles, and optionally a binder.

[0027] Cathode 12 may include other additives. Examples of these additives are disclosed in U.S. Pat. No. 5,342,712, which is therefore incorporated by reference. In certain embodiments, cathode 12 is preferably from about 0.2 weight percent about 2 weight percent of TiO ₂ (titanium dioxide), more preferably contains TiO ₂ of about 0.8 weight percent.

In some embodiments, cathode 12 may be a single pellet of material. Alternatively, the cathode 12 may be formed by a plurality of cathode pellets stacked on top of each other. In either case, the cathode pellets may be formed by first mixing manganese dioxide, carbon particles and an optional binder. For embodiments where one or more pellets are used, the mixture is pressed to form pellets. The pellets can be stored in the battery 10 using standard processes.
Is filled in. For example, in one process, a nucleus is positioned in the central cavity of the battery 10 and then a punch is used to pressurize the topmost pellet. When using this process, the outer wall 18 may have one or more vertical ridges annularly spaced along the outer wall 18 therein. These ridges may assist in holding the cathode 12 provided in the battery 10.

In embodiments where cathode 12 is formed from a single pellet, battery 10 may be directly filled with powder. To increase the packing density of the powder and form the cathode 12, a retaining ring may be fixed, or a drawing rod may pass through the retaining ring.

In some embodiments, a layer of conductive material may be provided between outer wall 18 and cathode 12. This layer may be disposed along the inner peripheral surface of the outer wall 18, the outer peripheral surface of the cathode 12, or both. Usually, this conductive layer is formed of carbonaceous material. This material is LB1000 (Timcal-), Electrodag (Electrodag) 112 (Acheson-Acheso)
n-) and EB0005 (Acheson). Methods for providing a conductive layer are disclosed, for example, in Canadian Patent No. 1,263,697, which is therefore treated as a reference.

Providing a conductive layer between the outer wall 18 and the cathode 12 fills the pellet (s) into the battery 10 when the cathode 12 is filled into the battery 10 by a pressurization process. Can be reduced. In this way, the porosity of the cathode 12 can be relatively increased without the pellets being crushed or cracking. However, if the porosity of the cathode 12 is too low, it will not be possible to disperse a sufficient amount of electrolyte within the cathode 12, resulting in reduced efficiency of the battery 10. Therefore, the cathode 12 should have a porosity of approximately 21% and 28%, more preferably a porosity of approximately 25% to approximately 27%, and most preferably a porosity of approximately 26%. is there.

When preparing the cathode 12, any of the conventional methods of forming manganese dioxide for the cathode can be utilized. Distributors of such manganese dioxide are Kerr Mcgee, Co., Broken Hill Proprietary (B
roken Hill Proprietary), Chem Metals, Co, Tosoh, Delta Manganese, Mitsui Chemicals and JMC.

In certain embodiments, cathode 12 may have from about 8.9 grams to about 9.8 grams of manganese dioxide. In these embodiments, cathode 12 preferably comprises from about 9.3 grams to about 9.75 grams of manganese dioxide, even more preferably from about 9.4 grams to about 9.65 grams of manganese dioxide; Most preferably, it contains from about 9.45 grams to about 9.6 grams of manganese dioxide.

In another embodiment, cathode 12 has a weight of about 4 grams to about 4.3.
Manganese dioxide, more preferably from about 4.05 grams to about 4.25 grams of manganese dioxide, and most preferably from about 4.1 grams to about 4.2 grams of manganese dioxide.

In certain embodiments where cathode 12 includes carbon particles, the carbon particles may be any of the standard carbon particles used in battery cathodes. Particle size is limited only by the size of the cathode. These may be synthetic or non-synthetic, and may have expandability or non-expandability. In certain embodiments, the carbon particles are non-synthetic, non-expandable graphite particles. In these embodiments, the graphite particles are:
Preferably less than about 20 microns, more preferably from about 2 microns to about 1 as measured using a Sympatec HELIOS analyzer.
It has an average particle size of 2 microns, most preferably about 5 to about 9 microns. Non-synthetic, non-expandable graphite particles include, for example,
It can be obtained from Brazilian National Graphite (Brazilian Nacional de Grafite) in Itapecirica, MG Brazil.

The amount of carbon particles in the cathode 12 should be large enough to improve the conductivity of the cathode 12 while having a minimal impact on the energy capacity of the battery 10. In certain embodiments, cathode 12 comprises about 4 to about 10 weight percent carbon particles, more preferably about 5 to about 9 weight percent carbon particles, and most preferably about 6 to about 8 weight percent. Contains carbon particles. These weight percentages correspond to the case where the electrolyte is not dispersed in the cathode 12.

In certain embodiments, cathode 12 may further include a binder. Examples of binders for cathode 12 include polyethylene powder, polyacrylamide, Portland cement, and fluorocarbon resins such as PVDF and PTFE. In one particular embodiment, cathode 12 comprises a polyethylene powder sold under the trade name coathylene HA-1861 (Hoescht).

When the cathode 12 includes a binder, the binder preferably comprises less than about 1 weight percent of the cathode 12, more preferably from about 0.1 weight percent to about 0.5 weight percent of the cathode 12. And most preferably to approximately 0.3 weight percent of cathode 12. These weight percentages correspond to when the electrolyte is not dispersed in cathode 12.

The anode 14 may be formed from any of the standard zinc materials used in battery anodes. Often, the anode 14 comprises a zinc metal powder,
It may be formed of a zinc gel containing a small amount of an additive such as a gelling agent and a gas generation inhibitor. Further, a portion of the electrolyte is dispersed throughout the anode 14.

If the porosity of the anode 14 is too high, the amount of zinc in the anode 14 is reduced to reduce the energy capacity of the battery 10. However, if the porosity of the anode 14 is too low, an insufficient amount of electrolyte will be dispersed within the anode 14. Thus, in one embodiment, the anode 14 preferably comprises about 2 grams of zinc particles per cubic centimeter of anode or 2.45 grams of zinc particles, more preferably about 2.1 grams of zinc particles per cubic centimeter of anode. Or about 2.35 grams of zinc particles, most preferably about 2.15 grams or about 2.3 grams of zinc particles per cubic centimeter of anode.

In certain embodiments, the anode 14 preferably has about 3.7 grams to about 4.25 grams of zinc particles, more preferably about 3.8 grams to about 4.15 grams of zinc particles, Most preferably, it contains about 3.9 grams to about 4.05 grams of zinc particles.

In another embodiment, anode 14 is preferably between about 1.5 grams and 1 gram.
. 9 grams of zinc particles, more preferably from about 1.55 grams to about 1.8
5 grams of zinc particles, most preferably from about 1.65 grams to about 1.7
Contains 5 grams of zinc particles.

In certain embodiments, the anode 14 preferably comprises about 64 to about 76 weight percent zinc particles, more preferably about 66 to about 74 weight percent zinc particles, and most preferably about 68 weight percent zinc particles. From about 72 weight percent zinc particles. These weight percentages correspond to those when the electrolyte was dispersed in the anode 14.

Gelled agents that can be used in anode 14 include polyacrylic acid, grafted starch material, salts of polyacrylic acid, polyacrylate, carboxymethylcellulose, or compounds thereof. Examples of these polyacrylic acids include Carbopol 940 (manufactured by BF Goodrich) and Polygel 4P (manufactured by 3V), and examples of grafted starch materials include Waterlock A221 (Grain Processing, Inc.). Muscatine, IA). An example of a salt of polyacrylic acid is CL15 (allide colloid). In certain embodiments, the anode 14 comprises from about 0.2 weight percent to about 1 weight percent of the total gelling agent, more preferably, from about 0.4 weight percent to about 0.7 weight percent of the total gelling agent. Preferably, it contains from about 0.5 to about 0.6 weight percent of the total gelling agent. These weight percentages correspond to when the electrolyte is dispersed throughout anode 14.

The gas generation inhibitor may be an inorganic material such as bismuth (blue lead), tin, lead, and indium. Alternatively, the gas generation inhibitor may be an inorganic compound such as a phosphate ester, an ionized surfactant and a non-ionized surfactant. Examples of ionized surfactants include, for example, US Pat. No. 4,777,100.
The disclosure of which is incorporated herein by reference.

The electrolyte dispersed throughout battery 10 may be any of the conventional electrolytes used in batteries. Usually, this electrolyte is a water-soluble hydroxide solution. Such a water-soluble hydroxide solution includes, for example, a hydroxide solution of potassium (potassium antimonate) and a hydroxide solution of sodium. In certain embodiments, the electrolyte is a water-soluble potassium hydroxide solution comprising about 33 to about 38 weight percent potassium hydroxide.

In certain embodiments, battery 10 preferably includes from about 3.4 grams to about 3.9 grams of electrolyte, and more preferably from about 3.45 grams to about 3.65 grams of electrolyte. And most preferably about 3.
It contains from 5 grams to about 3.6 grams of electrolyte.

In another embodiment, the battery 10 preferably contains from about 1.6 grams to about 1.9 grams of electrolyte, and more preferably from about 1.65 grams to about 1.85 grams of electrolyte. And most preferably from about 1.7 grams to about 1.8 grams of electrolyte.

The weight distribution ratio of manganese dioxide to electrolyte is from about 2.2 to about 2.9
And the weight distribution ratio of zinc particles to the electrolyte may be from about 0.9 to about 1.25. In some embodiments, the weight distribution ratio of manganese dioxide to electrolyte is preferably about 2.5 to about 2.9, and the weight distribution ratio of zinc particles to electrolyte is preferably about 1.1 to about 2.9. 1.25. In other embodiments, the weight distribution ratio of manganese dioxide to electrolyte is preferably from about 2.5 to about 2.65, and the weight distribution ratio of zinc particles to electrolyte is preferably from about 0.9 to about 0.9. It is about 1.2.

The batteries show excellent results when tested according to the cc photo test, 1 watt continuous test, half watt continuous test, pulsed test, half watt rm test and / or 1/4 watt rm test. (A) or A
An AA (triple A) battery may be used. These tests are described below.

The battery 10 may be an AA battery that shows excellent results when tested according to the one watt continuous test (described below). For example, when discharged to 1 volt according to a 1 watt continuous test, the AA battery has at least 0.6 hours, at least 0.65 hours, at least 0.7 hours, or at least 0.7 hours.
Pulses for 5 hours may be output. When discharged to 0.8 volts according to the 1 watt continuous test, the AA battery may output pulses for at least 0.95 hours, at least 1 hour, at least 1.05 hours, or at least 1.1 hours. good.

[0052] Battery 10 may be an AA battery that shows excellent results when tested according to the pulsed test (described below). For example, an AA battery may output pulses for at least 1.6 hours, at least 1.75 hours, at least 2 hours, or at least 2.15 hours when discharged to 1 volt according to a pulsed test. When the AA battery outputs at least 2.75 hours, at least 3 hours, at least 2.75 hours, or at least 3.3 hours of pulses when discharged to 0.9 volts according to the pulsed test good.

Battery 10 may be an AA battery that provides excellent performance when tested according to the half watt rm test (described below). For example, half watt r
AA batteries have at least 1.
5 hours, at least 2 hours, at least 2.5 hours, or at least 2.65
A pulse corresponding to time may be output. When discharged to 0.8 volts according to the half watt rm test, the AA battery has at least 2.9 hours, at least 3 hours,
Pulses for at least 3.25 hours or at least 3.4 hours may be output.

The battery 10 may be an AA battery that provides excellent performance when tested according to the half watt rm test (described below). For example, when discharged to 1.1 volts according to the half-watt continuous test, the AA battery has at least 1.5 hours, at least 2 hours, at least 2.5 hours, or at least 2.
A pulse for 65 hours may be output. When discharged to 0.8 volts according to the half watt rm test, the AA battery outputs pulses for at least 2.9 hours, at least 3 hours, at least 3.25 hours, or at least 3.4 hours. May be.

[0055] Battery 10 may be an AAA battery that exhibits excellent results when tested according to the half-watt continuous test (described below). For example, when discharged to 1 volt according to a half-watt continuous test, an AAA battery will have at least 0.
Pulses for 65 hours, at least 0.7 hours, at least 0.75 hours, or at least 0.8 hours may be output. When discharged to 0.9 volts according to the half-watt continuous test, the AAA battery outputs at least 0.9, at least 0.95, at least 1.0, or at least 1.1 hours of pulses. May be.

The battery 10 may be an AAA battery that provides excellent performance when tested according to a pulsed test (described below). For example, when discharged to 1 volt according to the pulsed test, the AAA battery has at least 0.35
Hours, at least 0.4 hours, at least 0.45 hours, or at least 0.4 hours.
A pulse for 5 hours may be output. When discharged to 0.9 volts according to the pulsed test, the AAA battery has at least 0.65 hours and at least 0,5 hours.
Pulses for 7 hours, at least 0.75 hours, or at least 0.8 hours may be output.

Battery 10 may be an AAA battery that provides excellent performance when tested according to the half-watt rm test (described below). For example, when discharged to 1.1 volts according to the half watt rm test, the AAA battery outputs at least 0.4 hours, at least 0.45 hours, at least 0.5 hours, or at least 0.55 hours of pulses. May be. When discharged to 0.9 volts according to the half watt rm test, the AAA battery may output pulses for at least 0.9 hours, at least 0.95 hours, at least 1 hour, or at least 1.05 hours. good.

Battery 10 may be an AAA battery that provides excellent performance when tested according to the ワ ッ ト watt rm test (described below). For example, 1 /
An AAA battery may output pulses for at least 2 hours, at least 2.1 hours, at least 2.2 hours, or at least 2.3 hours when discharged to 1.1 volts according to a 4 watt rm test. . When discharged to 0.9 volts according to the 1/4 watt rm test, the AAA battery has at least 3.1
Hours, at least 3.25 hours, at least 3.4 hours, or at least 3.
Pulses for 5 hours may be output.

Example I An AA battery was provided with the following components: The cathode is approximately 9.487
Gram of manganese dioxide (from Kelly-McGee, Co.) and an average particle size of 7 microns (National Graphite, Brazil-Brazilian Nacional de)
Approximately 0.806 grams of non-synthetic, non-expandable graphite
Approximately 0.3 weight percent ethylene copolymer material HA-1681. The anode contains approximately 3.976 grams of zinc particles, approximately 50 ppm of a sulfuractant associated with zinc (RM510, RM 510, Rhone Poulenc-), and approximately 0.5 weight percent total. And a gelling agent (Carbopol 940-Carbopol 940- and A221). The porosity of the cathode was approximately 26% and the porosity of the anode was such that it contained 2.173 grams of zinc per cubic centimeter of anode. The separator is composed of approximately 57 weight percent PVA fibers (approximately 0.5 denier at 6 millimeters) and approximately 30 weight percent rayon fibers (approximately 1.5 denier at 6 millimeters). PV
It had a two-layer structure including an A binder. Each layer was approximately 5.4 mm thick when dry and approximately 10 mm thick when wet. Each layer had a basis weight of approximately 54 grams per square meter. The separator did not contain any adhesive, and these layers did not substantially contain any filler. The battery also contained approximately 3.598 grams of a water soluble potassium hydroxide (approximately 35.5 weight percent potassium hydroxide) solution. A thin coating of EB005 (from Acheson) is placed between the outer wall of the battery and the outer periphery of the cathode.

The AA battery was stored at a temperature of approximately 20.1 ° C. to 22.1 ° C. for 5 days. The AA battery was further stored according to the following procedure.

Each battery is visually inspected for leaks and material damage and is treated the same to maintain battery identity throughout the test program. These batteries have their side walls oriented on the holding tray so that they do not make physical contact with each other. The holding trays are spaced so that the gap between the partitions between the upper and lower or adjacent trays is at least 5 cm (2 inches). As shown in Table I, the following 24-hour continuous test is repeated for 14 days.

[0062]

[Table 1] The trays are removed from the storage room and each battery is visually inspected for leaks and material impact.

The following tests were subsequently performed on individual AA batteries. Each test was performed at a temperature of approximately 20.1 ° C to 22.1 ° C.

The AA battery has a constant current state of 1 hour per day and 10 seconds per minute (“c
c Photographic test ") and discharged at an open circuit voltage of approximately 1.6 volts. The AA battery reached 1 volt after 192 pulses and reached 0.8 volts after 443 pulses.

The AA battery continuously discharged an open circuit voltage of approximately 1.6 volts at 1 watt (“1 watt continuous test”). The AA battery reached 1 volt after 0.75 hours and reached 0.8 volt after 1.00 hours.

The AA battery discharges in an open circuit of approximately 1.6 volts at a rate (“pulsing test”) that switches between 1 watt (3 second pulse) and 0.1 watt (7 second pulse). Continued. The AA circuit reached 1 volt after approximately 2.16 hours and reached 0.8 volt after approximately 3.72 hours.

The AA batteries discharged at an open circuit voltage of approximately 1.6 volts at 0.5 watts for 15 minutes per hour (“half watt rm test”). The AA battery reaches 1.1 volts after approximately 1.87 hours, and reaches 0.9 volts after approximately 3.34 hours.
The bolt has been reached.

Example II An AAA battery was prepared. The cathode 12 has approximately 4.155 grams of manganese dioxide (Kerr-McGee, Co.) and an average particle size of 7 microns (Brazilian Nacional de Grafite).
About 0.353 grams of non-synthetic non-expandable graphite and
3% by weight of an ethylene copolymer material HA-1681. The anode 14 comprises approximately 1.668 grams of zinc particles and approximately 50 zinc associated
ppm sulfactant (RM510, Loan Pollenk)
RM 510, Rhone Poulenc-) and approximately 0.5 weight percent of total gelling agents (Carbopol 940-Carbopol 940- and A221). The porosity of the cathode was approximately 26% and the porosity of the anode was such that it contained 2.266 grams of zinc per cubic centimeter of anode 14. The separator included multiple layers of nonwoven material. The separator is approximately 57
A two-layer structure comprising each of weight percent PVA fibers (about 0.5 denier at 6 millimeters) and about 30 weight percent rayon fibers (about 1.5 denier at 6 millimeters), and about 13 weight percent PVA binder. Met. Each layer was approximately 5.4 mm thick when dry and approximately 10 mm thick when wet. Each layer had a basis weight of approximately 54 grams per square meter. The separator contained no adhesive and these layers were substantially free of any filler. The battery also contained approximately 1.71 grams of a water soluble potassium hydroxide (approximately 35.5 weight percent) solution. A thin coating of EB005 (from Acheson-Acheson-) was placed between the outer wall of the battery and the outer periphery of the cathode.

The AAA batteries were stored as described in Example I. Each AA
A battery was discharged in an open circuit of approximately 1.6 volts and these tests
The test was performed within the temperature range described in the above.

An AAA battery is approximately 1.6 at one half watt (“half watt continuous test”)
Discharge continued at an open circuit voltage of volts. The AAA battery reached 1 volt after approximately 0.76 hours and reached 0.8 volts after approximately 0.96 hours.

For the pulsed test, the AAA battery took approximately 0.55 hours to reach 1 volt and 0.84 hours to reach 0.8 volts.

For the watt rm test, the AAA battery took approximately 0.57 hours to reach 1 volt and approximately 1.08 hours to reach 0.8 volts.

AAA batteries run at 0.25 watts for 15 minutes per hour (１ ／ watt rm
During the test, the battery was discharged from an open circuit voltage of about 1.6 volts. The AAA battery reached 1.1 volts after approximately 2.4 hours, and reached 0.9 volts after approximately 3.65 hours.

[0074] Other embodiments are within the scope of the following claims.

[Brief description of the drawings]

FIG. 1 is a longitudinal sectional view showing an alkaline battery according to an embodiment of the present invention.

FIG. 2 is a longitudinal sectional view of a separator.

FIG. 3 is a front view of a nonwoven material.

[Explanation of symbols]

 10 Battery 12 Cathode 14 Anode

──────────────────────────────────────────────────続 き Continuation of front page (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE ), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, KE , KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, UZ, VN, YU, ZW (72) Inventor George, Eye. Tay United States of America North Carolina, Waxhoe, Spruce, Pine, Trail, 7105 (72) Inventor Barbara, Bryce Massachusetts, United States of America, Bedford, Waite, Road, 24 (72) Inventor James, Seaveira, Massachusetts, United States of America Crestview, Avenue, 7 (72) Inventor Terry, El. Hamilton Drive, Tucom, Danbury, Connecticut, United States of America, 3 (72) Inventor Martin, AW. Howard Fairfield, Brooklyn, Parkway, Connecticut, USA 98 (72) Inventor Gregory, A. Faris, New York, USA, Poughkeepsie, Todd, Hill, Road, 57F term (reference) 5H021 CC02 EE05 EE11 HH01 HH03 5H024 AA01 AA03 AA14 DD09 DD14 EE09 HH01 HH13

Claims (27)

[Claims] 1. An electrochemical cell having a major axis and at least one minor axis orthogonal to the major axis, comprising: an anode, a cathode, and a separator disposed between the anode and cathode. An electrochemical cell comprising: a length direction of a fiber, at an angle within about 10 degrees with respect to a direction parallel to the long axis of the electrochemical cell, and at least about 60 degrees in a length direction of the fiber. %
An electrochemical cell, comprising: a first non-woven non-membrane material having a length, and a second non-woven non-membrane material disposed along a surface of the first material. 2. The electrochemical cell according to claim 1, wherein the separator is not a membrane material. 3. The electrochemical cell according to claim 1, wherein the separator has no adhesive material provided between the first and second nonwoven non-membrane materials. 4. The electrochemical cell according to claim 1, wherein the first and second nonwoven non-membrane materials are intersected. 5. The electrochemical cell according to claim 1, wherein said first nonwoven non-membrane material does not include any filler. 6. The electrochemical cell according to claim 1, wherein said second nonwoven non-membrane material does not include any filler. 7. The electrochemical cell of claim 1, wherein said first and second non-woven non-membrane materials each have at least about 20 basis weights. 8. The electrochemical cell according to claim 1, wherein said first and second nonwoven non-membrane materials each have a thickness of at least about 4 mm. 9. The electrochemical cell according to claim 1, wherein said first and second nonwoven non-membrane materials are formed of different sheet materials. 10. The electrochemical cell according to claim 1, wherein the first nonwoven non-membrane material includes a matrix of polyvinyl alcohol fibers, cellulose fibers, and a polyvinyl alcohol binder. 11. The electrochemical cell according to claim 1, wherein said first and second nonwoven non-membrane materials are capable of absorbing substantially the same amount of electrolyte. 12. The electrochemical cell according to claim 1, wherein the electrochemical cell is an alkaline battery. 13. The electrochemical cell according to claim 1, wherein the electrochemical cell is selected from the group consisting of an AA battery, an AAA battery, an AAAA battery, a C battery, and a D battery. 14. The electrochemical cell of claim 1, wherein said cathode is non-synthetic, non-expandable graphite particles having an average particle size of at most less than about 20 microns. 15. The electrochemical cell according to claim 1, wherein the cathode comprises manganese dioxide and carbon particles and the cathode has a porosity of approximately 21% to 28%. 16. The method of claim 1, wherein the anode comprises zinc particles and the anode has a porosity of about 2 grams to about 2.45 grams of zinc particles per cubic centimeter of anode volume. An electrochemical cell as described. 17. The electrochemical cell further comprising an electrolyte, wherein the cathode comprises manganese dioxide and a weight distribution ratio of manganese dioxide to the electrolyte is from about 2.2 to about 2.9. The electrochemical cell according to claim 1, wherein 18. The electrochemical cell further comprising an electrolyte, wherein the anode comprises zinc particles and a weight distribution ratio of the zinc particles to the electrolyte is from about 0.9 to about 1.2.
The electrochemical cell according to claim 1, wherein 19. A non-woven non-membrane material without any filler and a second non-woven non-membrane material disposed along a surface of the first non-woven non-membrane material. It is a battery separator provided, Comprising: The said battery separator does not contain a film material, The battery separator characterized by the above-mentioned. 20. The battery separator according to claim 19, wherein said second nonwoven non-membrane material does not include a filler. 21. The battery separator according to claim 19, wherein said separator does not include an adhesive material between first and second nonwoven non-membrane materials. 22. The battery separator of claim 19, wherein said first and second nonwoven non-membrane materials each have a basis weight of at least about 20. 23. The battery separator according to claim 19, wherein said first and second nonwoven non-membrane materials each have a thickness of at least about 4 millimeters. 24. The battery separator according to claim 19, wherein said first and second nonwoven non-membrane materials are formed of sheets of different materials. 25. The battery separator according to claim 19, wherein the first nonwoven non-membrane material includes a matrix of polyvinyl alcohol fibers, cellulose fibers, and a polyvinyl alcohol binder. 26. The battery according to claim 19, wherein the battery separator is in contact with an electrolyte.
A battery separator according to claim 1. 27. The battery separator of claim 19, wherein said first and second nonwoven non-membrane materials are capable of absorbing substantially the same amount of electrolyte.