WO2002007237A2 - Gel-forming battery separator - Google Patents
Gel-forming battery separator Download PDFInfo
- Publication number
- WO2002007237A2 WO2002007237A2 PCT/US2001/022090 US0122090W WO0207237A2 WO 2002007237 A2 WO2002007237 A2 WO 2002007237A2 US 0122090 W US0122090 W US 0122090W WO 0207237 A2 WO0207237 A2 WO 0207237A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- particles
- porous support
- gel
- forming
- battery separator
- Prior art date
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
- H01M10/08—Selection of materials as electrolytes
- H01M10/10—Immobilising of electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/443—Particulate material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
- H01M50/434—Ceramics
- H01M50/437—Glass
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- Valve regulated (“sealed”) lead acid (VRLA) batteries are known. These batteries include a plurality of positive and negative plate electrodes, as in a prismatic cell, or include layers of separator and electrode tightly wound together, known as “jelly roll” cells. The electrodes within a battery are arranged so that they alternate, negative-positive-negative, etc., with separator material between adjacent plates.
- the separator typically composed of a mat of fiberglass, serves several purposes. These include to retain electrolyte and to electrically insulate one electrode from the other. In addition, the partial saturation of the separator allows for void spaces through which gaseous oxygen may be transferred from a positive electrode, where it is generated, to a negative one, where it is consumed and reincorporated into the electrolyte. This is generally referred to as the internal oxygen cycle.
- the electrolyte should be immobilized. There are two known techniques to achieve this goal. One consists of absorbing the electrolyte within a fine fiber absorbent separator; the other is solidifying/gelling it by reaction with fine particles of, typically, fumed or colloidal silica. In this latter technique, the battery requires microporous separators to keep opposing electrodes apart. Various aspects regarding the process of gelling the electrolyte cause practical difficulties.
- Two processes are currently available to the battery manufacturer to produce batteries with gelled electrolyte.
- One process entails assemblage of a battery with its plates already electrochemically charged, followed by filling the battery with an electrolyte having a specific gravity in the range of 1.240-1.260. Approximately 6%-9% of fine silica particles are then added to the electrolyte. To prevent gel formation, the mixture must be kept continuously stirred and/or chilled 15-20 degrees Celsius below the ambient temperature. Once filled, the batteries are recharged and the electrolyte specific gravity rises to a range between 1.270 and 1.300.
- the second process includes the assembly of a battery with electrochemically uncharged plates.
- the plates are then treated with an electrolytic solution with specific gravity in the range of 1.200-1.240 to "form" the battery. Following formation, the battery is completely discharged. In this state, the sulfate content of the plates is known to be quite high.
- the electrolytic solution used during formation is then removed and the battery is refilled with a mix of sulfuric acid solution, with specific gravity in the range of 1.050-1.100, and 12%- 18% (by weight) of fine silica particles.
- the battery is then recharged. Upon completion of recharging, the electrolyte/silica will be gelled. The electrolyte specific gravity will have reached a level of 1.280-1.300.
- the invention provides, in accordance with a first embodiment, a method for constructing a gel-forming battery separator.
- Particles are embedded into pores of a porous support to form a composite.
- the chemical make-up of surfaces of the particles includes a silanol group.
- the composite is contacted with an effective amount of liquid electrolyte.
- Such contact of the composite with the electrolyte is capable of forming a gelled matrix that includes electrolyte residing within the porous support.
- the particles may be fumed silica particles; the electrolyte may be sulfuric acid.
- the effective amount of sulfuric acid may be determined such that the fumed silica particles, by weight, constitute in the range of about six percent to ten percent of the weight of the sulfuric acid.
- Embedding may involve placing particles adjacent the porous support and applying a mechanical force to the porous support. This force may be applied by calendering. Alternatively, particles may be embedded by electrostatically precipitating the particles upon the porous support.
- Embedding may instead involve applying the particles to a side of the porous support and applying a vacuum to an opposite side of the porous support.
- Gel-forming battery separators constructed by the above-described methods represent additional embodiments of the present invention.
- a battery including a container, a plurality of alternating positive and negative electrodes disposed within the container; and gel-forming separators disposed between the plurality of positive and negative electrodes.
- Each gel-forming separator has a porous support and particles embedded within the porous support. The particles have surfaces comprising a silanol group. These particles are capable of forming a gelled matrix comprising electrolyte within the porous support.
- a method of forming a battery is provided. Gel-forming battery separators are placed between pairs of electrodes residing in a container, each separator having a porous support; and embedded particles within pores of the support. The particles have surfaces chemically comprising a silanol group.
- Liquid electrolyte is added to the container, the liquid electrolyte having a specific gravity below a predetermined value required to form a gelled matrix when in contact with the separators.
- the electrodes are then charged to form the battery. Charging causing an increase in the specific gravity to the value required to form the gelled matrix. If the particles are fumed silica and the liquid electrolyte is sulfuric acid, the value required to form the gelled matrix is about 1.28.
- Gel-forming battery separators having a porous support and embedded particles having surfaces chemically comprising a silanol group are provided in additional embodiments.
- the porous support may be a woven or a nonwoven fabric.
- the nonwoven fabric may be polypropylene or polyester.
- the porous support may be a glass fiber support, more specifically, with borosilicate fiber.
- the porous support may have pores measuring in the range of about 10 microns to 100 microns.
- the particles may be silica, fumed silica, mica, silicate, polysilicate, or alumina silica. More specifically, fumed silica particles may have a size in the range of about 5 nm to 25 nm. Particles may have a surface area in the range of about 175 m 2 /g to 225 mVg.and may have a density of about 30 g/1.
- Figure 1 depicts a graphical representation of the formation of a battery of in accordance with an embodiment of the invention.
- FIG. 2 is a graphical representation comparing discharge rates of a battery, in accordance with an embodiment of the invention with a conventional glass mat formed battery.
- battery separator or “separator” are terms recognized in the art and are intended to mean devices located between positive electrodes and negative electrodes to act as physical and electrical barriers to prevent short-circuiting therebetween. Further NRLA battery separators hold an electrolyte thereon to enable a desired electromotive reaction.
- porous and microporous are recogmzed in the art and are intended to describe materials that have a plurality of interconnected interstices. These interconnected interstices admit passage of gas or liquid and, more generally provide communication both within and external to a structure made from the material.
- a porous support is part of a gel-forming battery separator in accordance with embodiments.
- the support may be made of a woven fabric or from a nonwoven material.
- woven fabric is art recognized and refers to the weaving of fibers (e.g., polymer resin fibers) into a fabric by conventional weaving techniques.
- nonwoven is art recognized and is intended to include those fibrous materials which are generally melt blown or spun bonded (e.g., extruded onto a moving web on a conveyer belt.)
- nonwoven materials may be prepared by what is known in the art as a "wet laid” process, whereby a flocculated mixture of fibers is passed through a screen/sieve with the removal of water.
- non woven materials can be prepared by a "dry laid” process such as carding. Any such non woven supports may additionally be bonded by thermal, chemical or mechanical (needling or hydroentangling) means for improved stiffness.
- particles having a surface silanol group includes those compositions that have silanol groups present on the surface of the particles. Suitable examples include variants of polymeric resins and siliceous materials that can hydrogen bond to water, such as variants of silica, mica, montmorilonite, asbestos, talc, diatomaceous earth, vermiculite, synthetic and natural zeolites, Portland cement, silicates, polysilicates, alumina silica and glass particles.
- an effective amount is intended to mean that amount of liquid electrolyte (such as sulfuric acid) necessary to be in contact with particles having a surface silanol group, required to create a gel entrapping/immobilizing electrolyte(s) within the separator. This amount will vary depending upon the chemistry of the particles and the specific gravity of acid; a skilled artisan can determine what ratio of percentage of particles to acid is required to cause gelation to occur.
- liquid electrolyte such as sulfuric acid
- the surface silanol groups react, under sufficiently acidic conditions to form a crosslinked, perhaps siloxane-based polymeric network that tends to immobilize or trap electrolyte.
- Such a network also provides channels to facilitate ion migration that leads to electric flow.
- a gel-forming composite battery separator includes a porous support with particles having surface silanol groups (e.g. fumed silica particles) embedded within the pores of the support.
- surface silanol groups e.g. fumed silica particles
- the porous support must be able to withstand a harsh chemical environment created by the presence of liquid electrolytes such as sulfuric acid.
- the porous support is a nonwoven material; however it could also be a woven fabric.
- the fiber diameter may range from about 5 microns to 30 microns, more specifically between about 20 to 25 microns.
- the fiber diameter of a fabric-based porous support is at least about 500 times larger than the diameter of the particles enmeshed throughout the porous structure of the support material.
- the porous support might be an open cell polymer foam having a pore size from about 1 to 300 microns, more specifically between about 50 to 100 microns.
- the interstices of the support wall comprise a void volume of at least about twenty percent of the support. The greater the void volume is, the better. Generally, a support should have as much as about ninety-seven percent void volume.
- Suitable polymeric materials for porous supports include but are in no way limited to, polyolefins such as polyethylene, polypropylene, polyisobutylene, and ethylene-alpha-olefin copolymers; acrylic polymers and copolymers such as polyacrylate, polymethylmethacrylate, polyethylacrylate; polyvinyl ethers such as polyvinyl methyl ether; polyacrylonitrile; polyvinyl ketones; polyvinyl aromatics such as polystyrene; polyvinyl esters, such as polyvinyl acetate; copolymers of vinyl monomers with each other and olefins, such as ethylene-methyl methacrylate copolymers, acrylonitrile-styrene copolymers, ABS resins, and ethylene-vinyl acetate copolymers; natural and synthetic rubbers, including butadiene-styrene copolymers, polyisoprene, synthetic polyisoprene
- the porous support may be formed from a chemically resistant glass fiber composition, such as a borosilicate glass fiber mat or C-glass.
- a chemically resistant glass fiber composition such as a borosilicate glass fiber mat or C-glass.
- C- glass chemical glass
- Such glass fiber compositions often contain zinc oxide as well as other oxides which make the fibers more resistant to chemical destruction.
- Typical commercially available C-glass fibers have compositions which include from about 65 to about 75% SiO 2 , from about 2 to about 6% Al 2 O 3 , from about 4 to about 14% CaO, from about 0 to about 5% MgO, from about 2 to about 7% B 2 O 3 , from about 9 to about 13% Na j O/K ⁇ O, from about 1 to about 6% ZnO, and from about 0%to trace amounts of FeO/Fe 2 O 3 .
- the porous support may also be a combination of glass fibers and polymeric fibers. The porous support provides strength and stiffness to the composite separator. The support may also be foldable.
- the porous support has a weight basis in the range of about 30 g/m 2 to 200 g/m 2 , more specifically about 100 g/m 2
- the thickness o.f the porous support is in the range of 1 to 10 mm, more specifically in the range of about 2 to 3 mm prior to , if desired, compression of the ultimate separator. If the composite separator is to be compressed, its final thickness will be in the range of about 1.5 to 2 mm.
- Particles with surfaces having a silanol group are embedded/enmeshed within the porous structure of the porous support. That is, the particles are trapped within high loft porous support materials, such that the particles are uniformly dispersed throughout the open celled structure of the porous support. It has been found that very fine particles embedded within the interstices of the support provide the most advantageous battery separators, although larger sized particles are not outside the scope of the present invention.
- suitable ranges for particles are in the range of about 5 nm to 25 nm.
- Suitable particles have a surface area in the range of about 175 m 2 /g to 225 m /g, and preferably about 200 m /g. Additionally, the particles generally can have a density of about 30 g/1.
- the ratio of the weight of particulates to the weight basis of the support is at least 50%. In general, it is desirable to maximize this ratio.
- the siliceous material is silica.
- Silica can take on many forms; however, fumed silica is used in the present invention as the particulate because of its active silanol groups.
- Suitable fumed silicas include those available from Cabot Corporation and referred to as CAB-O-SIL, untreated fumed silica (CAS No. 112945-52-5, Cabot Corporation, Cab-O-Sil Division, 700 E. U.S. Highway 36, Tuscola, Illinois) or Degussa-Huls Corporation referred to as Aerosil (Aerosil 200, BET surface 193 m 2 /g, Degussa-Huls Corporation, Waterford, NY).
- silanol groups on different particles react under acidic conditions to form a cross-linked network.
- the siloxane cross-linkage is a compound of silicon and oxygen in which each atom of silicon is bonded to four oxygen atoms, forming a tetrahedral structure, in a manner analogous to the bonding of carbon to hydrogen in methane, the bonds being of about the same strength in each case.
- This structure is found in the dioxide and in silicates generally, where the SiO4 groups occur in chains or rings.
- the silica component constitutes less than about 30% of the electrolyte's (in this case, sulfuric acid) weight.
- the particles with surface silanol groups may constitute a range of at least 6% to about 10% of the electrolyte's weight, and most specifically about a 6% ratio to sulfuric acid at a specific gravity of about 1.280. Increasing the specific gravity of the sulfuric acid will cause gelation, however, a specific gravity of below about 1.26 will not cause gelation.
- Suitable methods to embed the particles, within the pores of the material include mechanical force, such as a direct application of pressure to a layer of particles disposed on or adjacent to the support. Alternatively, the particles may be blown into the support and trapped. The resultant composite can be calendered, thereby compressing the porous support about the entrapped particles. Still another method to entrap the particles is by electrostatic precipitation. This process is based on the technology developed and patented by Electrostatic Technology, Inc. (Electrostatic Technology, Inc., 4 Pin Oak Drive, Branford, CT) where particulate material is applied to a porous substrate. The particles are aerated in a fluidizing chamber and are electrostatically charged by ionized air.
- the porous support is passed through the cloud of charged particles.
- the charged particles are attracted to the support and become embedded within the porous structure.
- particles are applied to one side of the porous support and a vacuum is applied to the opposite side of the porous support. The particles are then distributed throughout the porous structure of the porous support by the suctioning of the particles through the matrix of open pore cells throughout the porous support.
- a way is thus provided, in accordance with an exemplary embodiment, to suspend the dry particles in a three dimensional environment prior to treatment with sulfuric acid, or another liquid electrolyte.
- Addition of an effective amount of sulfuric acid to the particles embedded within the porous support causes a gelling reaction. It has been determined that a reaction occurs when fumed silica is exposed to sulfuric acid having at least 1.28 specific gravity.
- the sulfuric acid electrolyte is then incorporated within the formed gelatinous matrix. When this is performed within a battery, the porous support and particles therein, envelop the anode and cathode.
- electrochemical energy via ions e.g., the electrolyte which includes sulfuric acid, sulfate ion, water, hydronium ion, hydroxide ion, etc.
- Specific gravity of the sulfuric acid electrolyte is known to increase as a lead- acid battery is charged. Sulfate ions from the battery electrodes are released, causing the increase. At about a specific gravity of 1.28, the fumed silica particles and the electrolyte form a gelled matrix within the porous support. Alternatively, the particles may be exposed to sulfuric acid having a specific gravity above about 1.29 which results in gelation without the requirement of first charging of the battery.
- electrodes and separators may be installed into a battery container and introduced to sulfuric acid at a specific gravity of less than 1.28.
- fumed silica particles merely adsorb/absorb the electrolytic solution.
- the acidic solution causes the particles to gel, thereby causing the electrolyte(s) to become enmeshed within the gel and forming the composite about electrodes where it was placed.
- the resultant battery has a uniform distribution of gelled electrolyte material about and between the electrodes.
- the sulfuric acid component in the electrolytic solution has a concentration in the range of about 30 to 50% of the total volume of the solution. This figure is calculated using sulfuric acid which has a specific gravity of about 1.400 before mixing. More specifically, the sulfuric acid concentration may be in the range of about 43 to 48%o of the total volume of the solution.
- An alternative method of measuring an appropriate amount of sulfuric acid in the electrolyte is to measure the specific gravity after mixing the sulfuric acid into the electrolyte. By this method, the sulfuric. acid component should have a specific gravity in the range of about 1.200 to 1.390, and, more specifically, in the range of about 1.28 to 1.29. The following example serves to illustrate a specific embodiment.
- a battery was prepared with 3 positive and 4 negative plates.
- the battery separator of the invention was prepared by taking 24 cm by 13cm sheets having a weight basis range of about 3.04 to 3.76 g of polyester nonwoven (Hollingsworth & Nose 7333, a polyester nonwoven having a weight basis of 95 g/m 2 , thickness of 2.3 mm, and Frazier permeability of 279 ccs; available from Hollingsworth & Nose Company, East Walpole, Massachusetts) and embedding into the nonwoven in the range of about 1.86 to 2.62 g of fumed silica (See Tables 1 and 2) by mechanically pounding the silica into the nonwoven.
- the amount of silica used was approximately 6% of the electrolyte weight when a specific gravity of 1.28 was achieved.
- HONO-SOL denotes the gelled electrolyte battery separator(s)
- Formation of the battery was achieved by adding sulfuric acid to the battery and passing electric current through the cells for a period of about 60 hours.
- the final specific gravity of the fully formed battery was 1.28 to 1.29.
- the battery was sealed and included one-way valves to allow for internal oxygen recycling. During formation, the specific gravity was raised from an initial reading of 1.24 to 1.28 to 1.29.
- the voltage profile of the battery is shown in Figure 1.
- the gelled battery separator afforded similar electrical outputs to the control, standard absorbent glass mat (AGM) battery.
- AGM absorbent glass mat
- the gel battery outperformed the AGM by a considerable margin.
- the electrical output of the gelled battery was nearly twice that of a similar AGM battery. This behavior is in part explained by the better formation of the prototype battery.
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/069,817 US7097939B2 (en) | 2001-07-13 | 2001-07-13 | Gel-forming battery separator |
AU2001273438A AU2001273438A1 (en) | 2000-07-13 | 2001-07-13 | Gel-forming battery separator |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US21794400P | 2000-07-13 | 2000-07-13 | |
US60/217,944 | 2000-07-13 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2002007237A2 true WO2002007237A2 (en) | 2002-01-24 |
WO2002007237A3 WO2002007237A3 (en) | 2002-08-01 |
Family
ID=22813120
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2001/022090 WO2002007237A2 (en) | 2000-07-13 | 2001-07-13 | Gel-forming battery separator |
Country Status (2)
Country | Link |
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AU (1) | AU2001273438A1 (en) |
WO (1) | WO2002007237A2 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008077391A1 (en) * | 2006-12-22 | 2008-07-03 | White Fox Technologies Ltd | Fuel cell |
CN102290610A (en) * | 2011-07-15 | 2011-12-21 | 山东圣阳电源股份有限公司 | Colloidal storage battery formation method |
US9741989B2 (en) | 2004-10-01 | 2017-08-22 | Asahi Kasei Chemicals Corporation | Polyolefin microporous membrane |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1383190A (en) * | 1920-05-29 | 1921-06-28 | Demetreos J Demas | Tire |
US3351495A (en) * | 1966-11-22 | 1967-11-07 | Grace W R & Co | Battery separator |
US4150199A (en) * | 1977-05-05 | 1979-04-17 | Accumulatorenfabrik Sonnenschein Gmbh | Precursor for an electrical storage lead battery |
US4317872A (en) * | 1980-04-25 | 1982-03-02 | Gould Inc. | Lead acid battery with gel electrolyte |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10255752A (en) * | 1997-03-14 | 1998-09-25 | Japan Storage Battery Co Ltd | Separator for sealed type lead storage battery |
-
2001
- 2001-07-13 WO PCT/US2001/022090 patent/WO2002007237A2/en active Application Filing
- 2001-07-13 AU AU2001273438A patent/AU2001273438A1/en not_active Abandoned
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1383190A (en) * | 1920-05-29 | 1921-06-28 | Demetreos J Demas | Tire |
US3351495A (en) * | 1966-11-22 | 1967-11-07 | Grace W R & Co | Battery separator |
US4150199A (en) * | 1977-05-05 | 1979-04-17 | Accumulatorenfabrik Sonnenschein Gmbh | Precursor for an electrical storage lead battery |
US4317872A (en) * | 1980-04-25 | 1982-03-02 | Gould Inc. | Lead acid battery with gel electrolyte |
Non-Patent Citations (1)
Title |
---|
PATENT ABSTRACTS OF JAPAN vol. 1998, no. 14, 31 December 1998 (1998-12-31) & JP 10 255752 A (JAPAN STORAGE BATTERY CO LTD;G S KASEI KOGYO KK), 25 September 1998 (1998-09-25) * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9741989B2 (en) | 2004-10-01 | 2017-08-22 | Asahi Kasei Chemicals Corporation | Polyolefin microporous membrane |
US10384426B2 (en) | 2004-10-01 | 2019-08-20 | Asahi Kasei Chemicals Corporation | Polyolefin microporous membrane |
WO2008077391A1 (en) * | 2006-12-22 | 2008-07-03 | White Fox Technologies Ltd | Fuel cell |
CN102290610A (en) * | 2011-07-15 | 2011-12-21 | 山东圣阳电源股份有限公司 | Colloidal storage battery formation method |
Also Published As
Publication number | Publication date |
---|---|
AU2001273438A1 (en) | 2002-01-30 |
WO2002007237A3 (en) | 2002-08-01 |
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