CA2169954A1 - Improved battery plate and method of making - Google Patents
Improved battery plate and method of makingInfo
- Publication number
- CA2169954A1 CA2169954A1 CA 2169954 CA2169954A CA2169954A1 CA 2169954 A1 CA2169954 A1 CA 2169954A1 CA 2169954 CA2169954 CA 2169954 CA 2169954 A CA2169954 A CA 2169954A CA 2169954 A1 CA2169954 A1 CA 2169954A1
- Authority
- CA
- Canada
- Prior art keywords
- metallic fibers
- fibers
- battery plate
- metallic
- tow
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- 229920000914 Metallic fiber Polymers 0.000 claims abstract description 213
- 238000005253 cladding Methods 0.000 claims abstract description 101
- 239000000835 fiber Substances 0.000 claims abstract description 81
- 238000003860 storage Methods 0.000 claims abstract description 58
- 239000011148 porous material Substances 0.000 claims abstract description 43
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 43
- 239000011149 active material Substances 0.000 claims description 40
- 239000000463 material Substances 0.000 claims description 31
- 239000011159 matrix material Substances 0.000 claims description 20
- 229910052759 nickel Inorganic materials 0.000 claims description 20
- 238000005245 sintering Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims 5
- 238000000034 method Methods 0.000 description 55
- 238000000137 annealing Methods 0.000 description 17
- 239000002184 metal Substances 0.000 description 14
- 229910052751 metal Inorganic materials 0.000 description 14
- 238000010586 diagram Methods 0.000 description 10
- 238000009826 distribution Methods 0.000 description 5
- 239000007769 metal material Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 230000003028 elevating effect Effects 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- 239000006183 anode active material Substances 0.000 description 3
- 239000004917 carbon fiber Substances 0.000 description 3
- 239000006182 cathode active material Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229910001111 Fine metal Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 241001669026 Seison Species 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- 206010073099 Lobular breast carcinoma in situ Diseases 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 238000009960 carding Methods 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- 229940000425 combination drug Drugs 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000652 nickel hydride Inorganic materials 0.000 description 1
- 239000012254 powdered material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/80—Porous plates, e.g. sintered carriers
- H01M4/806—Nonwoven fibrous fabric containing only fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/002—Manufacture of articles essentially made from metallic fibres
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/80—Porous plates, e.g. sintered carriers
-
- 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
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/10—Battery-grid making
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249922—Embodying intertwined or helical component[s]
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2918—Rod, strand, filament or fiber including free carbon or carbide or therewith [not as steel]
- Y10T428/292—In coating or impregnation
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
- Y10T442/654—Including a free metal or alloy constituent
- Y10T442/655—Metal or metal-coated strand or fiber material
Abstract
An improved battery plate (40) and a method of making for an electric storage battery (10). The battery plate comprises a plurality of metallic fibers (50, 52) of a single or plural diameters (d, D) randomly oriented and sintered to provide a conductive battery plate with a multiplicity of pores defined therein (60). The metallic fibers are formed by cladding and drawing a plurality of metallic wires to provide a fiber tow. The fiber tow is severed and the cladding is removed to form metallic fibers. The metallic fibers are arranged into a web and sintered to form a battery plate.
Description
WO 9513S177 2 t 6- q q 5 ~ PCT/US95/07588 IMPROVED BATTERY PLATE AND METHOD OF MAKING
BACKGROUND OF THE INVENTION
Field of the Invention This invention relates to an improved battery plate for an electrical storage battery. More particularly, this invention relates to the method and apparatus of an improved battery plate fabricated with a fused web of metallic fibers.
Prior Art Statement For over one hundred years, electric storage batteries have provided portable and instantaneous electric power for a variety of electrical devices. Electric storage batteries include an anode and a cathode fabricated from dissimilar materials with an electrolyte interposed therebetween. An ionic exchange between the anode and thecathode through the electrolyte generates an electrical potential between the anode and the cathode. When the anode and the cathode are interconnected by an external load, an electric current is provided through a flow of ions through the electrolyte.
The electrical potential produced between the anode and the cathode is deter-mined by the rii~simil~r materials used for constructing the anode and the cathode.
The current produced by an electric storage battery is partially determined by the surface area of the anode and the cathode.
All electric storage batteries have an internal resistance which limits the 2n maximum current flow that can be generated by the electric storage battery. The maximum current flow that can be generated by the electric storage battery is common-Iy referred to as short circuit current. The short circuit current is the maximum current the electric storage battery can produce when the anode is externally shorted to the cathode with a large conductor.
In an effort to increase the surface area of the anode and the cathode, many electric storage batteries use a plurality of anode and cathode pairs within each battery cell. A separator is interposed between each anode and cathode pair with the anodes and cathodes being respectively connected in electrical parallel within each cell. The plurality of anode and cathode pairs within each battery cell increases the surface area of the anode and cathode for increasing the short circuit current of the cell.
In many cases, the anode and the cathode are each fabricated from a combina-tion of materials in an effort to reduce the weight and cost of the electric storage WOg~/35177 2 ~ ~ ~ 9 5 4 PCT/US95/07588 battery and to increase the efficiency thereof. In such cases, each of the anode and the cathode is fabricated with a conductive battery plate having a multiplicity of pores for receiving an active material therein.
Typically the battery plate is fabricated from a metallic material defining a 5 multiplicity of pores for receiving an active material therein. In some cases, the battery plate is fabricated from an in~ ting material coated with a conductive material. The insulating material defines a multiplicity of pores for receiving an active material therein.
The battery plate must be mechanically strong in order to m~int~in the active 10 material within the multiplicity of pores within the battery plate. Under certain conditions, a vibration and other mechanical impacts may cause the active material to dislodge or sepa,d~e from the battery plate thereby reducing efficiency of the electrical storage battery.
In some electric storage battery configurations, the battery plates including the 15 active material are rolled to form a cylindrical configuration to provide a cylindrically shaped electric storage battery. During the rolling process, the battery plates and the active material are subjected to substantial stresses during the rolling process. Any fracture of a portion of the battery plate will result in a reduced conductivity of the battery plate and accordingly a reduction in the current output of the electric storage 20 battery.
Many portable devices of the prior art utilize rechargeable batteries such as nickel cadmium, nickel hydride and other types of rechargeable batteries which enable the battery to be discharged and recharged hundreds or in some cases thousands of times. A rechargeable battery must be designed and fabricated to with~t~nd the 25 charging and recharging as well as an extended life of the rechargeable battery.
In addition, the prior art is striving to continue to reduce the weight of batteries in order to reduce the overall weight of many portable device such as radios, televi-sions, telephones, computers, games and the like. In order to reduce the weight of the battery, the prior art has utilized various materials for the battery plates of electric 30 storage batteries.
U.S. Patent 3,262,815 to Langer et. al. discloses an electrode suitable for a secondary battery comprising a plate formed from a compact body of intermingled fine wo 9S/3Sl77 Pcr/usss/07588 21 6~954 metal fibers, the majority of the fibers exten-ling the full height of the plate and a small proportion extending transverse thereto, the fine metal fibers having a generally parallel lineal orientation in one direction and an active electrode material distributed on and disposed within the body of the metal fibers, a liquid electrolyte permeable sheet 5 wrapping enclosing the plate, an electrical contact attached to the plate transverse to the general lineal orientation of the fine metal fibers whereby most of the fibers are directly connected thereto, an electrical lead attached to the electrical contact, and an insulated covering about the lead and the contact.
U.S. Patent 4,206,271 to Norling et. al. discloses a method for the manufacture 10 of a highly porous nickel electrode body for electrical accl-mlll~tors. The new elec-trode body is also disclosed. By using 5-7% volume of a nickel powder in ad~ ulewith 93-95% by volume of a pore-forming agent selected from the group consistingof amrnonium bicarbonate and ammonium carbonate when pressing and sintering the electrode body a very high porosity is obtained, such as 90-95%, in spite of which the 15 mechanical strength of the body is so high as to resist the strains of an accllm~ tor cell. Especially preferable to impart o~tst~n~ing strength to the electrode body, is a pressure of at least 100 MPa in the pressing operation.
U.S. Patent 4,251,603 to Matsumoto et. al. discloses a battery electrode compris-ing a plaque made of a sponge-like porous metal matrix having a multiplicity of cells 20 connected with each other in three--limensions, wherein the sectional area of the gratings making up the sponge-like metal porous plaque decreases continuously along the thickness of the plaque from the surface toward the central part and an active material is impregnated in the porous plaque.
U.S. Patent 4,628,593 to Fritts et. al. discloses a low shear battery plaque and25 a nickel electrode fabricated therefrom, the latter consisting es~enti~lly of a centrally located layer of a conductive felt, layers of sintered nickel on each side of the felt and nickel hydroxide active material disposed throughout the pores of the sintered nickel.
U.S. Patent 5,080,963 to Tatarchuk et. al. discloses a new class of composite results from a matrix of carbon fibers, including graphite fibers, interwoven in a 30 network of fused metal fibers. The composites can be fabricated to have varying surface area, void volume and pore size while m~int~ining high electrical conductivity.
Composites are readily p,~l)aled from a ~ulerollll of a dispersion of carbon fibers, metal 2 t 6 ~ 9 5 4 PCT/US95/07588 fibers, and an organic binder such as cellulose, by heating the plerol", at a ~lllp~ Lul~
sufficient to fuse the metal fibers and to volatilize at least 90% of the binder with a loss of less than about 25~G, and usually under 10%, by weight of carbon fiber.
U.S. Patent 5,106,707 to Catotti et. al. discloses a sealed rechargeable nickel 5 electrode containing an electrochemical cell having a pasted negative electrode with paste layers adhered to a nonforminous conductive substrate, which retards growth (swelling) of the nickel electrode on cycling.
U.S. Patent 5,200,281 to Leap et. al. discloses a sintered bipolar battery plate(10) which is made containing two porous electrodes and a central, non-porous, 10 metallic cell sepa, al~ i-current collector sheet (12) where the positive electrode contains sintered particles (14) of elemental silver sintered into an expanded metal sheet (18) and the negative electrode contains sintered particles (16) of elemental iron sintered into an expanded metal sheet (18), where the positive and negative electrodes are sintered to a thin, porous, metallic connection layer (20) selected from at least one of 15 nickel fiber or nickel powder, which is sinlt;lcd to the current collector (12). This plate (10) can be placed in a case (22) cont~ining alkali hydroxide electrolyte and having metal end plates (29) for electrical connections.
U.S. Patent 5,200,282 to Masuhiro et. al. discloses a nickel electrode for use in an ~lk~line battery using a network-like ~lk~line-proof metal mesh having pores at 20 the inside thereof as a core metal current collector, as well as an ~lk~line battery using such a nickel electrode. Inexpensive nickel electrode having high performance, great capacity can be obtained at high productivity.
U.S. Patent 5,244,758 to Bronoel et. al. discloses a positive nickel electrode having a structure of cellular nickel foam filled with a paste based on nickel hydrox-25 ide. The paste contains (in dry matter and per 100 parts by weight nickel hydroxide)7 to 8 parts by weight powder-form nickel metal, 5 to 12 parts by weight of a cobalt hydroxide and/or salt, the parts by weight being expressed as equivalents of cobalt metal.
Although the aforementioned prior art have advanced the battery art, there is 30 a need for further advancement in the battery art especially in the fabrication of the battery plates therefore.
W0 95/35177 ~ t ~ 9 q 5 ~ PCT/US551'U7S88 .
Therefore, it is an object of this invention to provide an improved battery plate for an electric storage battery fabricated of a matrix of randomly oriented metallic fibers wherein the metallic fibers are fused to adjacent fibers to provide an electrically conductive porous battery plate with a high total energy density as well as high5 strength.
Another object of this invention is to provide an improved battery plate for an electric storage battery fabricated of a matrix of randomly oriented metallic fibers wherein the metallic fibers are sintered to fuse the metallic fibers into an electrically conductive porous battery plate.
Another object of this invention is to provide an improved battery plate for an electric storage battery fabricated of a sintered matrix of randomly oriented metallic fibers wherein each of the metallic fibers have a subst~nti~lly equal length and a substantially uniform cross-sectional area.
Another object of this invention is to provide an improved battery plate for an 15 electric storage battery fabricated of a sintered matrix of randomly oriented m~t~llic fibers wherein each of the metallic fibers has a subst~nti~lly cylindrical shape for increasing the surface area of the battery plate.
Another object of this invention is to provide an improved battery plate for an electric storage battery fabricated of a sintered matrix of randomly oriented rnt-t~llic 20 fibers for providing a multiplicity of pores defined between adjacent fibers.Another object of this invention is to provide an improved battery plate for an electric storage battery fabricated of a sintered matrix of randomly oriented metallic fibers for providing a multiplicity of pores defined belweell adjacent fibers for inter-locking an active plate material into the multiplicity of pores of the battery plate.
2~ Another object of this invention is to provide an improved battery plate for an electric storage battery fabricated of a sintered matrix of randomly oriented met~llic fibers for providing a battery plate wherein the porosity of the battery plate can be accurately controlled.
Another object of this invention is to provide an improved battery plate for an 30 electric storage battery fabricated of a sintered matrix of randomly oriented m~t~llic fibers comprising a multiplicity of major di~n~eter fibers and a multiplicity of minor rii~meter fibers sintered to provide a highly conductive battery plate.
WO 95/35177 2 ~ ~ ~ q 5 4 PCT/U~55~ 7~1s8 Another object of this invention is to provide an improved battery plate for an electric storage battery fabricated of a sintered matrix of randomly oriented mPt~llic fibers with increased porosity and increased conductivity over the battery plates known to the prior art.
Another object of this invention is to provide an improved battery plate for an electric storage battery fabricated of a sintered matrix of randomly oriented metallic fibers having a higher porosity and capable of receiving substantially more active plate material than the battery plates of the prior art.
Another object of this invention is to provide an improved battery plate for an electric storage battery fabricated of a sintered matrix of randomly oriented metallic fibers having a porosity of greater than 9S percent.
Another object of this invention is to provide an improved battery plate for an electric storage battery fabricated of a sintered matrix of randomly orient~l metallic fibers which may be rolled in a cylindrical configuration without deterioration of the lS electrical contact or bond between adjacent fused metallic fibers.
Another object of this invention is to provide an improved battery plate for an electric storage battery fabricated of a sintered matrix of randomly oriented metallic fibers with the metallic fibers having one or more dia,l.~ uniformly distributedwithin the matrix.
Another object of this invention is to provide an improved battery plate for an electric storage battery fabricated of a sintered matrix of randomly oriented m~t~llic fibers wherein the metallic fibers may be pl~rt;-entially disposed in the battery plate for providing a substantially ullirOIlll current density throughout the battery plate.
The foregoing has outlined some of the more pertinent objects of the present invention. These objects should be construed as being merely illustrative of some of the more prominent features and applications of the invention. Many other beneficial results can be obtained by applying the disclosed invention in a dirr.,.~ t manner or modifying the invention within the scope of the invention. Accordingly other objects in a full understanding of the invention may be had by referring to the S~mm~ry of the invention, the detailed description describing the ple~lled embodiment in addition to the scope of the invention defined by the claims taken in conjunction with the accompanying drawings.
Wo95l35177 2 ~ 6 ~ ~ 5 4 PCT/US95/07588 SUMMARY OF THE INVENTION
The present invention is defined by the appended claims with specific embodi-ments being shown in the attached drawings. For the purpose of ~.,n.-.~.izing the invention, the invention relates to an improved battery plate for an electric storage 5 battery comprising a plurality of metallic fibers with the plurality of metallic fibers being substantially randomly oriented in a web. Each of the plurality of metallic fibers is fused to an adjacent one of the plurality of metallic fibers for forming a conductive battery plate with a multiplicity of pores defined therein.
In a more specific embodiment of the invention, each of the plurality of metallic 10 fibers has a substantially cylindrical shape with a major diameter with each of the plurality of metallic fibers having a length at least one thousand times the major diameter. Preferably, the plurality of metallic fibers comprises a plurality of major diameter metallic fibers and a plurality of minor diameter metallic fibers. The major diameter metallic fibers have a diameter at least twice the diameter of each of the 15 minor diameter fibers.
In one embodiment of the invention, the plurality of metallic fibers are substan-tially randomly oriented within the web in multiple planes with each of the plurality of metallic fibers being fused to adjacent metallic fibers by sintering the web. The plurality of metallic fibers are flexible for providing a flexible battery plate. The 20 plurality of metallic fibers are resilient for resiliently interlocking an active plate material into the multiplicity of pores of the battery plate.
The invention is also inc."~old~ed into the method of making a battery plate for an electric storage battery, comprising the steps of forming a tow of metallic fibers and severing the tow of metallic fibers. The severed metailic fibers are formed into 25 a web and the metallic fibers are opened to provide loose metallic fibers. The loose metallic fibers are fused within the web in a sintering process to form a battery plate.
In a more specific embodiment of the method of the invention, the step of forming a tow of metallic fibers includes cladding and drawing a plurality of metallic wires for providing a drawn cladding with a reduced diameter and removing the 30 cladding to provide the fiber tow. The metallic fibers are drawn to have a substantially cylindrical shape with a major diameter. The tow of metallic fibers is severed to provide met~llic fibers having a length at least one thousand times the major diameter.
Wo95/35177 ~ 1 6~54 PCrlU595107588 In one embodiment of the invention, a portion of the tow of metallic fibers are formed to have a major ~i~m~ter and a portion of the tow of metallic fibers are formed to have a minor diameter with the major diameter being at least twice the minor ~i~meter. The metallic fibers are fused within the web by sintering the web for 5 providing an electrically conductive battery plate having a multiplicity of pores therein with a high mechanical strength.
The foregoing has outlined rather broadly the more pertinent and important features of the present invention in order that the let~ile-l description that follows may be better understood so that the present contribution to the art can be more fully 10 appreciated. Additional features of the invention will be described hereinafter which form the subject of the claims of the invention. lt should be appreciated by those skilled in the art that the conception and the specific embodiment~ disclosed may be readily utilized as a basis for modifying or designing other structures for carrying out the same purposes of the present invention. It should also be realized by those skilled 15 in the art that such equivalent constructions do not depart from the spirit and scope of the invention as set forth in the appended claims.
wo 95135177 2 t 6 ~ ~ 5 ~ PCT/US95/07588 BRIEF DESCRIPTION OF THE DRA~1VINGS
For a fuller understanding of the nature and objects of the invention, referenceshould be made to the following detailed description taken in connection with the accompanying drawings in which:
FIG. 1 is an isometric view of an example of an electric storage battery;
FIG. 2 is an isometric view of a partially rolled electric storage battery of FIG.
I illustrating an anode battery plate, a cathode battery plate and a separator;
FIG. 3 is a magnified partial view of the battery plate of the present invention suitable for use with the electric storage battery of FIG. l;
FIG. 4 is a nl~gnified partial view similar to FIG. 3 of the battery plate of the present invention with an active plate material thereon;
FIG. 5 is a block diagram of a first method of producing a fiber tow for fabricating a first embodiment of the battery plate shown in FIGS. 3 and 4;
FIG. 5A is an enlarged cross-sectional view of the Clad 1, Single Wire in FIG.
5;
FIG. SB is an enlarged cross-sectional view of the Multiple Draw and Anneal in FIG. 5;
FIG. 5C is an enlarged cross-sectional view of the Clad 2, Multiple Clad 1 in FIG. 5;
FIG. SD is an enlarged cross-sectional view of the Multiple Draw and Anneal in FIG. 5;
FIG. SE is an enlarged cross-sectional view of the Clad 3, Multiple Clad 2 in FIG. 5;
FIG. SF is an enlarged cross-sectional view of the Multiple Draw and Anneal in FIG. 5;
FIG. 6 is a block diagram of a second method of producing a fiber tow for fabricating a second embodiment of the battery plate shown in FIGS. 3 and 4;
FIG. 6A is an enlarged cross-sectional view of the Clad 1, Single Wire in FIG.
6;
FIG. 6B is an enlarged cross-sectional view of the Multiple Draw and Anneal in FIG. 6;
Wo 95135177 ~ t ~ 9 9 ~ 4 PCT/U~g ~ 8 FIG. 6C is an enlarged cross-sectional view of the Additional Draw and Anneal in FIG. 6;
FIG. 6D is an enlarged cross-sectional view of the Clad 2, Multiple Clad 1 in FIG. 6;
FIG. 6E is an enlarged cross-sectional view of the Multiple Draw and Anneal in FIG. 6;
FIG. 6F is an enlarged cross-sectional view of the Clad 3, Multiple Clad 2 in FIG. 6;
FIG. 6G is an enlarged cross-sectional view of the Multiple Draw and Anneal in FIG. 6;
FIG. 7 is a block diagram of the method of making a web of metallic fibers;
FIG. 8 is a diagram of the process for separating and randomly orienting the metallic fibers to form a web; and FIG. 9 is a block diagram of the method of making the electric storage battery of FIG. 1.
Similar reference characters refer to similar parts throughout the several Figures of the drawings.
WO 95/3S177 ~ 9 5 ~ PCT/US95/07588 .
DETAILED DISCUSSION
FIG. 1 is an isometric view of an example of an electric storage battery 10 of the present invention. FIG. 2 illustrates the internal configuration of the electric storage battery 10 of FIG. 1. The electric storage battery l0 comprises an anode 11 and a cathode 12 with a sepa.~tor 13 interposed therebetween. The anode 11, the cathode 12 and the separator 13 are established in an adjacent relationship and rolled to form a cylindrical battery configuration. The anode 11 and the cathode 12 arerespectively connected to anode and cathode terminals 16 and 18 by conventional means (not shown) as should be well known in the art. The anode 11 comprises an anode plate 21 constructed of a porous material with an anode active material 31disposed in the pores of the anode plate 21. The cathode 12 comprises a cathode plate 22 constructed of a porous material with a cathode active material 32 disposed in the pores of the cathode plate 22. The anode active material 31 and the cathode active material 32 is commonly referred to as a battery paste. The anode plate 21 and the 15 cathode plate 22 are constructed of a conductive material for providing electrical conductivity between the anode active material 31 and the cathode active material 32 with the anode plate 21 and the cathode plate 22, respectively, as should be well known to those skilled in the art.
FIG. 3 is a m~gnified view of a portion of the improved battery plate 40 of the present invention comprising a plurality of metallic fibers 50. Each of the plurality of metallic fibers 50 is formed of a flexible and resilient solid metallic material for providing a flexible battery plate 21. The type of metallic material used for forming the battery plate 40 is selected by the type of battery to be constructed as well as the active material used and the polarity of the battery plate.
Each of the plurality of metallic fibers 50 has a substantially cylin-lric~l shape with a major diameter D and a substantially uniform length L. Preferably, each of the plurality of metallic fibers 50 has a length L at least one thousand times the major diameter D. As shown in FIG. 3, the plurality of metallic fibers 50 are substantially randomly oriented in multiple planes of the battery plate 40. Each of the plurality of metallic fibers 50 is fused to an adjacent one of the plurality of metallic fibers 50 for forming the conductive battery plate 40 with a multiplicity of pores 60 defined therein.
The plurality of met~llic fibers 50 are fused to adjacent metallic fibers 50 in the same WO 9S/35177 ~ t ~ PCTIUS95/07588 plane as well as adjacent planes of the multiple layer battery plate 40 to form a three ~imen~ional metallic fiber matrix having multiple layers of adjacent metallic fibers 50 with the multiplicity of pores 60 defined therein. Preferably, the plurality of metallic fibers 50 are fused to adjacent metallic fibers 50 by a sintering process.
S Optionally, the plurality of mPt~llic fibers 50 comprises a nli~ule of a plurality of major diameter metallic fibers 51 and a plurality of minor diameter metallic fibers 52. Each of the plurality of major metallic fibers 51 has a major diameter (D) and a substantially uniform length (L). Each of the plurality of minor metallic fibers 52 has a minor diameter (d) and a substantially uniform length (l). Preferably, the major In diameter metallic fibers 51 having a major diameter (D) at least twice the minor diameter (d) of each of the minor diameter fibers 52. The length L of each of the plurality of major metallic fibers 51 is equal to the length (1) of each of the plurality of minor diameter metallic fibers 52.
In one example of the invention, the plurality of major metallic fibers 51 and 15 the plurality of minor metallic fibers 52 are formed of a nickel metallic material. The plurality of major m~t~llic fibers 51 have a major diameter (D) of 4.0 microns and a substantially uniform length (L) of 2.54 centimeters. The plurality of minor metallic fibers 52 have a minor diameter (d) of 2.0 microns and a substantially unirollll length (I) of 2.54 ce~,~;r"eL~,~. The specific ratio of the plurality of major m.ot~llic fibers 51 20 to the plurality of rninor metallic fibers 52 may be determined by the desired porosity of the battery plate 40, the metallic materials used and the process for making the metallic fibers 50.
FIG. 4 is a m~gnified view similar to FIG. 3 illustrating the improved battery plate 40 of FIG. 3 with the active material 65 thereon. The active material 65 is 25 pressed into the pores 60 in the battery plate 40 in a conventional manner. The plurali-ty of metallic fibers 50 are resilient for resiliently interlocking the active plate material 65 into the multiplicity of pores 60 of the battery plate 40. In addition, the plurality of metallic fibers 50 resiliently interlock the active material 65 within the multiple layers of adjacent fibers 50.
The cylinrlric~l shape of adjacent metallic fibers 50 create generally wedge-shape regions which entrap the active material 65 for insuring that the active m~teri~l 65 is maintained in electrical conductivity with the battery plate 40 during vibration, wo95135177 ~ 5~ PCT/U~5~1~/5~8 shock and the like. It is further believed that during the pasting process, the resilient metallic fibers resiliently deform when the active material 65 is pressed within the battery plate 40 by an external pressure. The resilient deformation of the metallic fibers 50 produces a resilient bias which resiliently maintains the active material 65 within the battery plate 40. The resilient bias continues to maintain the active material 65 within the battery plate 40 as the active material 65 is depleted from the battery plate 40. As the active material 65is depleted from the battery plate 40, the resiliency bias of the metallic fibers 50 return the metallic fibers 50 toward a non-deformed condition which maintains the engagement of the metallic fibers 50 with the active material 65. The resiliency bias of the metallic fibers 50 insure that the active material 65 m~int~in~ in electrical conductivity with the battery plate 40 even after substantial depleion of the active material 65.
FIG. 5 is a block diagram of a first method of producing a fiber tow for fabricating a first embodiment of the battery plate shown in FIGS.3 and 4. The first method of making a fiber tow provides uniform rli~m~t~r metallic fibers from a metallic wire 1 10 through the use of a first, second and third cladding 111-113. The metallic wire 110 is selected to be resistant to a removal process such as being resistant to a selected acid or as being resistant to a selected electrolysis process.
FIG.5 illustrates a first cladding process 121 for cladding the metallic wire 110 with a cladding material 116 to provide the first cladding 111. The cladding material 116 is selected to be removable in a removal process such as being soluble in a selected acid or as being removable in a selected electrolysis process as will be described in greater detail hereinafter. Preferably, the cladding material 116is a strip of material that is bent to l-ilcu-nscribe the outer diameter 1 lOD of the metallic wire 110.
FIG. 5A is a cross-sectional view of the first cladding 111 having an outer diameter 11 lD. Preferably, the first cladding 111 is continuously passed through the annealing oven having an inert atmosphere.
FIG.5 illustrates a drawing and annealing process 122 of the first cladding 111.Preferably, the drawing and annealing process 122 of the first cladding 111 includes the successive drawing and ~nne~ling of the first cladding 111 for reducing the outer diameter l l lD.
Wo 95/35177 2 1 ~ ~ 9 5 ~ PCT/US95/07S88 FIG. 5B is a cross-sectional view of the first cladding 111 after passing through the drawing and annealing process 122.
FIG. 5 illustrates a second cladding process 123 for cladding a plurality of thefirst clafl-ling~ 111 with the cladding material 116 to provide the second cladding 112.
FIG. 5C is a cross-sectional view of the second cladding 112 illustrating a plurality of the first claddings 111 within the second cladding 112.
FIG. 5 illustrates a drawing and annealing process 124 of the second cladding 112. Preferably, the drawing and annealing process 124 of the second cladding 112 includes the successive drawing and annealing of the second cladding 112 for reducing the outer diameter 11 lD.
FIG. 5D is a cross-sectional view of the second cladding 112 after passing through the drawing and annealing process 124.
FIG. S illustrates a third cladding process 125 for cladding a plurality of the second claddings 112 with a cladding material 116 to provide the third cl~dding 113.
FIG. 5E is a cross-sectional view of the third cladding 113 illustrating a plurality of the second cla~-ling~ 112 within the third cladding 113.
FIG. 5 illustrates the drawing and annç~ling process 126 of the third cladding 113. Preferably, the drawing and anne~ling process 126 of the third cladding 113includes the successive drawing and annç~ling of the third cladding 113 for reducing the outer diameter 11 lD.
FIG. SF is a cross-sectional view of the third cladding 113 after passing through the drawing and annçaling process 126.
FIG. 6 is a block diagram of a second method of producing a fiber tow for fabricating a second embodiment of the b?ttery plate 40 shown in FIGS. 3 and 4. The second method of making a fiber tow provides major ~iamçter metallic fibers 141 and provides minor rliameter met~llic fibers 142 from a metallic wire 210 through the use of a first, second and third cladding 211-213.
FIG. 6A is a cross-sectional view of the first cladding 211 having an outer diameter 21 lD. Preferably, the first cladding 211 is continuously passed through the ~nnç~ling oven having an inert atmosphere.
FIG. 6 illustrates a drawing and annealing process 222 of the first cladding 211.
Preferably, the drawing and annç~ling process 222 of the first cladding 211 includes WO 95/35177 ~ ~ 6 9~ q 5 ~ PCT/US95/07588 the successive drawing and annealing of the first cladding 211 for reducing the outer diameter 21 lD.
After the first cladding 211 is passed through the drawing and annealing process222, the first cladding 211 is separated into a primary portion 241 and a secondary S portion 242. The secondary portion 242 of the first cladding 211 is passed through an additional draw and annealing process 222A for further reducing the outer rii~rneter 21 lD.
FIG. 6B is a cross-sectional view of the primary portion 241 of the first cladding 211 after passing through the drawing and ~nnçaling process 222. FIG. 6C
is a cross-sectional view of the secondary portion 242 of the first cladding 211 after passing through the additional drawing and ~nne~ling process 222A. The first cladding 211 in the primary portion 241 defines a major diameter whereas the first cladding 211 in the secondary portion 242 defines a minor (li~meter. The minor diameter of the secondary portion 242 of the first cladding 211 has a substantially smaller cross-sectional area relative to the major diameter of the primary portion 241 of the first cladding 211.
FIG. 6 illustrates a second cladding process 223 for cladding a plurality of theprimary portion 241 and a plurality of the secondary portions 242 of the first claddings 211 with a cladding material 216 to provide the second cladding 212.
FIG. 6D is a cross-sectional view of the second cladding 212 illustrating a plurality of the primary and secondary portions 241 and 242 of the first claddings 211 within the second cladding 212.
FIG. 6 illustrates a drawing and annealing process 24 of the second cladding 224. Preferably, the drawing and ~nne~ling process 224 of the second cladding 212 includes the successive drawing and ~nnç~ling of the second cladding 212 for reducing the outer rli~meter 211D.
FIG. 6E is a cross-sectional view of the second cladding 212 after passing through the drawing and annealing process 224.
FIG. 6 illustrates a third cladding process 225 for cladding a plurality of the second claddings 212 with a cladding material 216 to provide the third cladding 213.
FlG. 6F is a cross-sectional view of the third cladding 213 illustrating a plurality of the second claddings 212 within the third cladding 213.
WO 95/35177 PCr/uss5/07588 2~qq5~ ~
FIG. 6 illustrates a drawing and annealing process 226 of the third cladding 213.
Preferably, the drawing and annealing process 226 of the third cladding 213 includes the successive drawing and annç~ling of the third cladding 213 for reducing the outer diameter 21 lD.
FIG. 6G is a cross-sectional view of the third cladding 213 after passing through the drawing and annealing process 226.
FIG. 7 is a block diagram of the processing of the third cladding 213 to providea fiber tow 250 having the major diameter metallic fibers 141 and the minor ~ met--r metallic fibers 142. The third cladding 213 is passed through the severing device 271 I() for breaking the third cladding 213 into segment of a desired length. The severed segments of the third cladding 213 is subjected to the removing process 272 to remove the cladding material 216 to produce metallic fibers 270 of a desired length. The cladding removing process 272 may be a leaching process wherein the third cladding 213 is immersed into an acid for dissolving an acid soluble cladding material 216.
In the alternative, the removing process 272 may include an electrolysis process for removing the cladding m~t~ri~l 216.
The metallic fibers 260 comprises a plurality of major wire fibers 261 and a plurality of minor wire fibers 262. Each of the plurality of major wire fibers 261 has a major diameter whereas each of the plurality of minor wire fibers 262 has a minor ~ meter. The ratio of primary portion 241 to the secondary portion 242 in the second cladding 212 determines the ratio of the quantity of major wire fibers 261 to the quantity of the minor wire fibers 262.
After completion of the removing process 272, wire fibers 260 are separated or opened into individual loose metallic fibers 260. The individual loose metallic fibers 260 are subjected to an optional carder 274 for carding the wire fibers 260. Theoptional carder 274 bends each of the metallic fibers 260 to facilitate interconnection and interlinking when the metallic fibers 260 are formed into a web 280. The bends further facilitate the random orientation and substantially uniform distribution of the minor wire fibers 262 within the major wire fibers 261. The carded wire fibers 260 are formed into a web 280 by a weber 275.
FIG. 8 is a diagram of the process for separating and randomly orienting the met~llic fibers 260 to form a web 280. The substantially parallel metallic fibers 260 WO 95/35177 2 1 ~ ~ ~ 5 ~ PCTrUS95/07588 are placed in a hopper 300 and are conveyed by an inclined plane 302 to housing 304 containing a plurality of rollers 311-31~. The inclined plane 302 directs the m~t~llic fibers 260 to rotating opener rollers 311 and 312 for partially opening the metallic fibers 260. The partially opened metallic fibers 260 pass from the opposite rotating opener rollers 311 and 312 to the main opener cylinder 314. The rotating opener roller-313 returns excess metallic fibers 260 to the hopper 300. The partially opened metallic fibers 260 pass between the main opener cylinder 314 and a working roller 315 and a stripper roller 316 that cooperate with the main opener cylinder 314 for further opening and blending the metallic fibers 260. The opened and blended metallic fibers 0 260 are passed through an air roller 317 for subjecting the metallic fibers 260 to a high velocity air stream and for transferring the metallic fibers 260 through a conduit 318 to an air separator 320.
The air separator 320 further sep~tes and opens the metallic fibers 260 by high velocity air. The opened metallic fibers 260 settle onto a horizontal conveyor 321 and 15 are moved to an elevating conveyor 322. The metallic fibers 260 are passed between the elevating conveyor 322 and a ~ er conveyor 323 to return any excess of the opened metallic fibers 260 to the horizontal conveyor 321. The met~llic fibers 260 passing between the elevating conveyor 322 and the ~LIipp~l conveyor 323 are project-ed by the elevating conveyor 322 to a first condenser screen 325 and a plurality of 20 roller conveyors 326.
The first condenser screen 325 is provided with an air flow by a blower 330 througlh a suction duct 331 as in~lic~ted by the arrows. The air pressure above the first condenser screen 325 iS below atmospheric l~r~s~u.~ and accordingly the air flow passes through the first condenser screen 325 into the suction duct 331 as indicated by the 25 arrows to determine the quantity of the metallic fibers 260 attracted to the first condenser screen 325. As the metallic fibers 260 acc--mul~te on the first condenser screen 325, the air flow passing through the first condenser screen 325 iS proportionally reduced until an equilibrium is reached and a continuous and uniform mat of metallic fibers 332 are disposed upon the first condenser screen 325.
The uniform mat of metallic fibers 332 is moved over a feed plate 335 by feed rollers 336 to a lickerin 340. The uniform mat of metallic fibers 341 are combed by the lickerin 340 for producing individual met~llic fibers 260A. The individual metallic WO95135177 21 ~9~ PCTnJ~g~1~7588 ~
fibers 260A are directed by an air stream provided by a blower 341 and a pressure duct 342 to a second condenser screen 345. The velocity of the air stream generated by the blower 341 is controlled by an opening belwæll the lickerin 340 and a saber 346.
The saber 346 is mounted on an eccenL~ ic (not shown) for varying the opening between S the lickerin 340 and a saber 346 to control the air flow therethrough.
As the metallic fibers 260A accllm~ te on the second condenser screen 345, the air flow passing through the second condenser screen 345 is proportionally reduced until an equilibrium is reached and a continuous and uniform web of met~llic fibers 280 is disposed upon the second condenser screen 345. The uniform web of metallic fibers 280 is directed to an output conveyor 348 for completing the process of making the web 280.
FIG. 9 is a block diagram of the method of making the electric storage battery of FIG. 1. The web 280 is subjected to a sintering process 351 for fusing the metallic fibers 260 within the web 280. The web 280 subjected to a process 352 to form the battery plate 40. The battery plate 40 is passed through a pasting process 353 for adding the active material 65 to the battery plate 40. The pasted battery plate 40 is then processed through a final assembly 354 for adding the anode and cathode termi-nals 16 and 18.
The improved battery plate of the present invention has a number of advantages 20 over the battery plates of the prior art. Typically, the fibers forming the battery plate are normally 12 to 25 millimeters long with a ~ meter of 1.0 micron to 30.0 microns.
The metallic fibers are extremely strong and bend when the battery plate is rolled into a cylindrical configuration without any loss of conductivity of the metallic fibers.
Accordingly, each of the metallic fibers is assured electrical conductivity for a dimen-25 sion of 12 to 25 millimeters. In contrast, the battery plates of the prior art made of powdered materials is only assured electrical conductivity across the tli~met~or of the powdered particle. Although each of the metallic fibers has a relatively large linear dimension, it has a very small rli~meter dimension compared to metallic formed plates of the prior art. Accordingly, the electrical conductivity between the active material 30 and the battery plate in the present invention is much shorter in distance than the prior art metallic battery plates. Furthermore, as can be seen in Fig. 3, the metallic fibers ~WO 95/35177 2 1 ~ 5 4 PCTIUS95/07S88 form multiple layers in the matrix to further reduce the short distance between the active material and the battery plate.
Another advantage of the present invention is the maximum contact between adjacent metallic fibers at points along the respective length of each of the fibers in S the sintering process. Each of the metallic fibers has a cylindrical to cylinder contact with adjacent fibers which can be carefully controlled in the sintering oven to insure a proper fusing of the materials. The cylindrical to cylinder contact insures a high electrical conductivity between adjacent metallic fibers while allowing the improved battery plate to flex and bend for use in large variety of battery configurations.
A further advantage of the present invention is the multiple layers of the cylindrical fibers entrapping the active material therein. Adjacent cylindrical fibers form wedge-shape regions which entrap the active material therein for insuring that the active material is maintained in electrical conductivity with the battery plate through vibration, shock and the like. It is further believed that during the pasting process, the metallic fibers resiliently bend to accommodate for the active material when the active material is forced within the battery plate by an active ~les~ulc. This flexing of the metallic fibers produces a resiliency which resiliently holds the active material within the improved battery plate. Furthermore, it is further believed that as the active material is depleted from the battery plate, the resiliency of the metallic fibers urge the metallic fibers to the undistorted position which maintains the engage-ment with the active material to insure that the active material maintains the electrical conductivity with the battery plate even when the active material is substantially depleted. A battery plate 40 having a porosity of 95% to 98% is possible through the use of the present invention.
Table I illustrates the physical and electrical characteristics of four prior art battery plates used commercially in the art. The Celmet battery plate is constructed of a nickel foam material in accordance with the teaching of U.S. patents 4,251,603.
The Nihon Seison and Katayama battery plates are constructed of a nickel coated plastic material.
The specifications set forth in Table I are either the specifications of the manufacturers or are measured p~ ln(,LCIS. The resi~t~nce values set forth in Tables I and II were measured between two positions 10.0 ce..Lh--elels apart on a strip of WO95135177 2 1 6 9 9 5 ~ PCT/US95/07588 battery plate 1.0 centimeters wide and 12.0 centimet~rs in length. The ABS value of the pore size distribution indicates the maximum limiting pore di~mPter or the maxi-mum diameter of a particle that can pass through the battery plate. The percentage of the pore size distnbution 5 was determined by a wet flow test. The ~ entage of the pore size distribution indicates the pore size at which that percentage of flow is passing through pores of the indicated diameter or smaller.
The value for the ABS was determined by a wet bubble point test whereas the values for the 98%, 90% and 50% pore size distribution were statistically determined 10 by a combination of the wet bubble point test and a dry air flow test. The values of Tables I and II are believed to accurately refiect the true porosity and to provide a true companson of porosity values for the battery plates.
TABLE I
CHARACTERISTICS PRIOR ART BATTERY PLATES
MEDIA CELMET NIHON SEISON KATAYAMA
Porosity (%) 94.5 90.0 94.0 Base Weight (o%/yd2) 16.2 12.5 12.7 Thickness (mm) 1.5 1.0 1.2 Tensile Strength (psi) 170 120 168 Recic~ re (mS2) 39 80 83 Resistivity (mQ) 0.69 0.80 0.83 Pore Si%e Distribution (,um) AsS 265 180 215 98% 265 145 155 90% 260 125 125 50% 185 80 75 Table II illustrates the physical and electrical characteristics of the first embodi-ment of the improved battery plate 40 of the present invention. The eight types of specimens of the improved battery plate 40 were all made from 25 micron nickel fiber.
WO95/3S177 2 1 ~ ~ ~ 5 4 PCT~S95/07588 .
TABLE II
~CKEL ~BER BATTERY PLATE(25um) Porosity(%) 95% 95% 95.5 95.5 96.0 96.0 96.5 96.5 Base Weight (o~yd2) 13.5 17.5 13.5 17.5 13.5 17.5 13.5 17.5 Thic~ess (mm) 1,0 1.3 1 1 15 13 17 1 5 19 Tensile S~eng~ (psi) 230 230 210 210 180 180 165 165 Resis~nce (mn) 55 40 55 40 55 40 55 40 Res~vity (m~-cm) 0.75 0.47 0.83 0.54 0.98 0.61 1.13 0.69 Pore Size Distribution (~
98% 200 200 210 210 230 230 250 250 90~ 190 190 190 190 210 210 240 240 50% 125 125 125 125 135 135 160 185 A comparison of Table I and Table II reveals the superior performance of the improved battery plate 40 over the battery plates of the prior art. The improved battery plate 40 has superior resistivity, porosity and tensile strength over the battery plates of the prior art.
Typically, the volume of the battery plate is measured by a liquid displacement 20 process for determining the porosity of the battery plate. It should be realized that the porosity of the improved battery plate 40 is an accurate porosity since the metallic fibers 260 are solid fibers. In many cases, the stated porosity of the powdered or plated plastic battery plates of the prior art are inaccurate since the powdered or plated plastic materials have internal voids or filler materials of dir~c;nt densities that are 25 inc~p~hle of recelving active material. The porosities of Table I are based on estim~tes of the determined porosity values as set forth above. Accordingly, the performance - of the improved battery plate 40 over the battery plates of the prior art is believed to be as indicated in Tables I and II.
The present disclosure includes that contained in the appended claims as well 30 as that of the foregoing description. Although this invention has been described in its WO 95/3Sl77 2 1 6 ~ ~ 5 4 PCT/USg5/07588 ~
preferred form with a certain degree of particularity, it is understood that the present disclosure of the pre~l.ed forrn has been made only by way of example and that numerous changes in the details of construction and the combination and arrangement of parts may be resorted to without departing from the spirit and scope of the inven-5 tion.
BACKGROUND OF THE INVENTION
Field of the Invention This invention relates to an improved battery plate for an electrical storage battery. More particularly, this invention relates to the method and apparatus of an improved battery plate fabricated with a fused web of metallic fibers.
Prior Art Statement For over one hundred years, electric storage batteries have provided portable and instantaneous electric power for a variety of electrical devices. Electric storage batteries include an anode and a cathode fabricated from dissimilar materials with an electrolyte interposed therebetween. An ionic exchange between the anode and thecathode through the electrolyte generates an electrical potential between the anode and the cathode. When the anode and the cathode are interconnected by an external load, an electric current is provided through a flow of ions through the electrolyte.
The electrical potential produced between the anode and the cathode is deter-mined by the rii~simil~r materials used for constructing the anode and the cathode.
The current produced by an electric storage battery is partially determined by the surface area of the anode and the cathode.
All electric storage batteries have an internal resistance which limits the 2n maximum current flow that can be generated by the electric storage battery. The maximum current flow that can be generated by the electric storage battery is common-Iy referred to as short circuit current. The short circuit current is the maximum current the electric storage battery can produce when the anode is externally shorted to the cathode with a large conductor.
In an effort to increase the surface area of the anode and the cathode, many electric storage batteries use a plurality of anode and cathode pairs within each battery cell. A separator is interposed between each anode and cathode pair with the anodes and cathodes being respectively connected in electrical parallel within each cell. The plurality of anode and cathode pairs within each battery cell increases the surface area of the anode and cathode for increasing the short circuit current of the cell.
In many cases, the anode and the cathode are each fabricated from a combina-tion of materials in an effort to reduce the weight and cost of the electric storage WOg~/35177 2 ~ ~ ~ 9 5 4 PCT/US95/07588 battery and to increase the efficiency thereof. In such cases, each of the anode and the cathode is fabricated with a conductive battery plate having a multiplicity of pores for receiving an active material therein.
Typically the battery plate is fabricated from a metallic material defining a 5 multiplicity of pores for receiving an active material therein. In some cases, the battery plate is fabricated from an in~ ting material coated with a conductive material. The insulating material defines a multiplicity of pores for receiving an active material therein.
The battery plate must be mechanically strong in order to m~int~in the active 10 material within the multiplicity of pores within the battery plate. Under certain conditions, a vibration and other mechanical impacts may cause the active material to dislodge or sepa,d~e from the battery plate thereby reducing efficiency of the electrical storage battery.
In some electric storage battery configurations, the battery plates including the 15 active material are rolled to form a cylindrical configuration to provide a cylindrically shaped electric storage battery. During the rolling process, the battery plates and the active material are subjected to substantial stresses during the rolling process. Any fracture of a portion of the battery plate will result in a reduced conductivity of the battery plate and accordingly a reduction in the current output of the electric storage 20 battery.
Many portable devices of the prior art utilize rechargeable batteries such as nickel cadmium, nickel hydride and other types of rechargeable batteries which enable the battery to be discharged and recharged hundreds or in some cases thousands of times. A rechargeable battery must be designed and fabricated to with~t~nd the 25 charging and recharging as well as an extended life of the rechargeable battery.
In addition, the prior art is striving to continue to reduce the weight of batteries in order to reduce the overall weight of many portable device such as radios, televi-sions, telephones, computers, games and the like. In order to reduce the weight of the battery, the prior art has utilized various materials for the battery plates of electric 30 storage batteries.
U.S. Patent 3,262,815 to Langer et. al. discloses an electrode suitable for a secondary battery comprising a plate formed from a compact body of intermingled fine wo 9S/3Sl77 Pcr/usss/07588 21 6~954 metal fibers, the majority of the fibers exten-ling the full height of the plate and a small proportion extending transverse thereto, the fine metal fibers having a generally parallel lineal orientation in one direction and an active electrode material distributed on and disposed within the body of the metal fibers, a liquid electrolyte permeable sheet 5 wrapping enclosing the plate, an electrical contact attached to the plate transverse to the general lineal orientation of the fine metal fibers whereby most of the fibers are directly connected thereto, an electrical lead attached to the electrical contact, and an insulated covering about the lead and the contact.
U.S. Patent 4,206,271 to Norling et. al. discloses a method for the manufacture 10 of a highly porous nickel electrode body for electrical accl-mlll~tors. The new elec-trode body is also disclosed. By using 5-7% volume of a nickel powder in ad~ ulewith 93-95% by volume of a pore-forming agent selected from the group consistingof amrnonium bicarbonate and ammonium carbonate when pressing and sintering the electrode body a very high porosity is obtained, such as 90-95%, in spite of which the 15 mechanical strength of the body is so high as to resist the strains of an accllm~ tor cell. Especially preferable to impart o~tst~n~ing strength to the electrode body, is a pressure of at least 100 MPa in the pressing operation.
U.S. Patent 4,251,603 to Matsumoto et. al. discloses a battery electrode compris-ing a plaque made of a sponge-like porous metal matrix having a multiplicity of cells 20 connected with each other in three--limensions, wherein the sectional area of the gratings making up the sponge-like metal porous plaque decreases continuously along the thickness of the plaque from the surface toward the central part and an active material is impregnated in the porous plaque.
U.S. Patent 4,628,593 to Fritts et. al. discloses a low shear battery plaque and25 a nickel electrode fabricated therefrom, the latter consisting es~enti~lly of a centrally located layer of a conductive felt, layers of sintered nickel on each side of the felt and nickel hydroxide active material disposed throughout the pores of the sintered nickel.
U.S. Patent 5,080,963 to Tatarchuk et. al. discloses a new class of composite results from a matrix of carbon fibers, including graphite fibers, interwoven in a 30 network of fused metal fibers. The composites can be fabricated to have varying surface area, void volume and pore size while m~int~ining high electrical conductivity.
Composites are readily p,~l)aled from a ~ulerollll of a dispersion of carbon fibers, metal 2 t 6 ~ 9 5 4 PCT/US95/07588 fibers, and an organic binder such as cellulose, by heating the plerol", at a ~lllp~ Lul~
sufficient to fuse the metal fibers and to volatilize at least 90% of the binder with a loss of less than about 25~G, and usually under 10%, by weight of carbon fiber.
U.S. Patent 5,106,707 to Catotti et. al. discloses a sealed rechargeable nickel 5 electrode containing an electrochemical cell having a pasted negative electrode with paste layers adhered to a nonforminous conductive substrate, which retards growth (swelling) of the nickel electrode on cycling.
U.S. Patent 5,200,281 to Leap et. al. discloses a sintered bipolar battery plate(10) which is made containing two porous electrodes and a central, non-porous, 10 metallic cell sepa, al~ i-current collector sheet (12) where the positive electrode contains sintered particles (14) of elemental silver sintered into an expanded metal sheet (18) and the negative electrode contains sintered particles (16) of elemental iron sintered into an expanded metal sheet (18), where the positive and negative electrodes are sintered to a thin, porous, metallic connection layer (20) selected from at least one of 15 nickel fiber or nickel powder, which is sinlt;lcd to the current collector (12). This plate (10) can be placed in a case (22) cont~ining alkali hydroxide electrolyte and having metal end plates (29) for electrical connections.
U.S. Patent 5,200,282 to Masuhiro et. al. discloses a nickel electrode for use in an ~lk~line battery using a network-like ~lk~line-proof metal mesh having pores at 20 the inside thereof as a core metal current collector, as well as an ~lk~line battery using such a nickel electrode. Inexpensive nickel electrode having high performance, great capacity can be obtained at high productivity.
U.S. Patent 5,244,758 to Bronoel et. al. discloses a positive nickel electrode having a structure of cellular nickel foam filled with a paste based on nickel hydrox-25 ide. The paste contains (in dry matter and per 100 parts by weight nickel hydroxide)7 to 8 parts by weight powder-form nickel metal, 5 to 12 parts by weight of a cobalt hydroxide and/or salt, the parts by weight being expressed as equivalents of cobalt metal.
Although the aforementioned prior art have advanced the battery art, there is 30 a need for further advancement in the battery art especially in the fabrication of the battery plates therefore.
W0 95/35177 ~ t ~ 9 q 5 ~ PCT/US551'U7S88 .
Therefore, it is an object of this invention to provide an improved battery plate for an electric storage battery fabricated of a matrix of randomly oriented metallic fibers wherein the metallic fibers are fused to adjacent fibers to provide an electrically conductive porous battery plate with a high total energy density as well as high5 strength.
Another object of this invention is to provide an improved battery plate for an electric storage battery fabricated of a matrix of randomly oriented metallic fibers wherein the metallic fibers are sintered to fuse the metallic fibers into an electrically conductive porous battery plate.
Another object of this invention is to provide an improved battery plate for an electric storage battery fabricated of a sintered matrix of randomly oriented metallic fibers wherein each of the metallic fibers have a subst~nti~lly equal length and a substantially uniform cross-sectional area.
Another object of this invention is to provide an improved battery plate for an 15 electric storage battery fabricated of a sintered matrix of randomly oriented m~t~llic fibers wherein each of the metallic fibers has a subst~nti~lly cylindrical shape for increasing the surface area of the battery plate.
Another object of this invention is to provide an improved battery plate for an electric storage battery fabricated of a sintered matrix of randomly oriented rnt-t~llic 20 fibers for providing a multiplicity of pores defined between adjacent fibers.Another object of this invention is to provide an improved battery plate for an electric storage battery fabricated of a sintered matrix of randomly oriented metallic fibers for providing a multiplicity of pores defined belweell adjacent fibers for inter-locking an active plate material into the multiplicity of pores of the battery plate.
2~ Another object of this invention is to provide an improved battery plate for an electric storage battery fabricated of a sintered matrix of randomly oriented met~llic fibers for providing a battery plate wherein the porosity of the battery plate can be accurately controlled.
Another object of this invention is to provide an improved battery plate for an 30 electric storage battery fabricated of a sintered matrix of randomly oriented m~t~llic fibers comprising a multiplicity of major di~n~eter fibers and a multiplicity of minor rii~meter fibers sintered to provide a highly conductive battery plate.
WO 95/35177 2 ~ ~ ~ q 5 4 PCT/U~55~ 7~1s8 Another object of this invention is to provide an improved battery plate for an electric storage battery fabricated of a sintered matrix of randomly oriented mPt~llic fibers with increased porosity and increased conductivity over the battery plates known to the prior art.
Another object of this invention is to provide an improved battery plate for an electric storage battery fabricated of a sintered matrix of randomly oriented metallic fibers having a higher porosity and capable of receiving substantially more active plate material than the battery plates of the prior art.
Another object of this invention is to provide an improved battery plate for an electric storage battery fabricated of a sintered matrix of randomly oriented metallic fibers having a porosity of greater than 9S percent.
Another object of this invention is to provide an improved battery plate for an electric storage battery fabricated of a sintered matrix of randomly orient~l metallic fibers which may be rolled in a cylindrical configuration without deterioration of the lS electrical contact or bond between adjacent fused metallic fibers.
Another object of this invention is to provide an improved battery plate for an electric storage battery fabricated of a sintered matrix of randomly oriented metallic fibers with the metallic fibers having one or more dia,l.~ uniformly distributedwithin the matrix.
Another object of this invention is to provide an improved battery plate for an electric storage battery fabricated of a sintered matrix of randomly oriented m~t~llic fibers wherein the metallic fibers may be pl~rt;-entially disposed in the battery plate for providing a substantially ullirOIlll current density throughout the battery plate.
The foregoing has outlined some of the more pertinent objects of the present invention. These objects should be construed as being merely illustrative of some of the more prominent features and applications of the invention. Many other beneficial results can be obtained by applying the disclosed invention in a dirr.,.~ t manner or modifying the invention within the scope of the invention. Accordingly other objects in a full understanding of the invention may be had by referring to the S~mm~ry of the invention, the detailed description describing the ple~lled embodiment in addition to the scope of the invention defined by the claims taken in conjunction with the accompanying drawings.
Wo95l35177 2 ~ 6 ~ ~ 5 4 PCT/US95/07588 SUMMARY OF THE INVENTION
The present invention is defined by the appended claims with specific embodi-ments being shown in the attached drawings. For the purpose of ~.,n.-.~.izing the invention, the invention relates to an improved battery plate for an electric storage 5 battery comprising a plurality of metallic fibers with the plurality of metallic fibers being substantially randomly oriented in a web. Each of the plurality of metallic fibers is fused to an adjacent one of the plurality of metallic fibers for forming a conductive battery plate with a multiplicity of pores defined therein.
In a more specific embodiment of the invention, each of the plurality of metallic 10 fibers has a substantially cylindrical shape with a major diameter with each of the plurality of metallic fibers having a length at least one thousand times the major diameter. Preferably, the plurality of metallic fibers comprises a plurality of major diameter metallic fibers and a plurality of minor diameter metallic fibers. The major diameter metallic fibers have a diameter at least twice the diameter of each of the 15 minor diameter fibers.
In one embodiment of the invention, the plurality of metallic fibers are substan-tially randomly oriented within the web in multiple planes with each of the plurality of metallic fibers being fused to adjacent metallic fibers by sintering the web. The plurality of metallic fibers are flexible for providing a flexible battery plate. The 20 plurality of metallic fibers are resilient for resiliently interlocking an active plate material into the multiplicity of pores of the battery plate.
The invention is also inc."~old~ed into the method of making a battery plate for an electric storage battery, comprising the steps of forming a tow of metallic fibers and severing the tow of metallic fibers. The severed metailic fibers are formed into 25 a web and the metallic fibers are opened to provide loose metallic fibers. The loose metallic fibers are fused within the web in a sintering process to form a battery plate.
In a more specific embodiment of the method of the invention, the step of forming a tow of metallic fibers includes cladding and drawing a plurality of metallic wires for providing a drawn cladding with a reduced diameter and removing the 30 cladding to provide the fiber tow. The metallic fibers are drawn to have a substantially cylindrical shape with a major diameter. The tow of metallic fibers is severed to provide met~llic fibers having a length at least one thousand times the major diameter.
Wo95/35177 ~ 1 6~54 PCrlU595107588 In one embodiment of the invention, a portion of the tow of metallic fibers are formed to have a major ~i~m~ter and a portion of the tow of metallic fibers are formed to have a minor diameter with the major diameter being at least twice the minor ~i~meter. The metallic fibers are fused within the web by sintering the web for 5 providing an electrically conductive battery plate having a multiplicity of pores therein with a high mechanical strength.
The foregoing has outlined rather broadly the more pertinent and important features of the present invention in order that the let~ile-l description that follows may be better understood so that the present contribution to the art can be more fully 10 appreciated. Additional features of the invention will be described hereinafter which form the subject of the claims of the invention. lt should be appreciated by those skilled in the art that the conception and the specific embodiment~ disclosed may be readily utilized as a basis for modifying or designing other structures for carrying out the same purposes of the present invention. It should also be realized by those skilled 15 in the art that such equivalent constructions do not depart from the spirit and scope of the invention as set forth in the appended claims.
wo 95135177 2 t 6 ~ ~ 5 ~ PCT/US95/07588 BRIEF DESCRIPTION OF THE DRA~1VINGS
For a fuller understanding of the nature and objects of the invention, referenceshould be made to the following detailed description taken in connection with the accompanying drawings in which:
FIG. 1 is an isometric view of an example of an electric storage battery;
FIG. 2 is an isometric view of a partially rolled electric storage battery of FIG.
I illustrating an anode battery plate, a cathode battery plate and a separator;
FIG. 3 is a magnified partial view of the battery plate of the present invention suitable for use with the electric storage battery of FIG. l;
FIG. 4 is a nl~gnified partial view similar to FIG. 3 of the battery plate of the present invention with an active plate material thereon;
FIG. 5 is a block diagram of a first method of producing a fiber tow for fabricating a first embodiment of the battery plate shown in FIGS. 3 and 4;
FIG. 5A is an enlarged cross-sectional view of the Clad 1, Single Wire in FIG.
5;
FIG. SB is an enlarged cross-sectional view of the Multiple Draw and Anneal in FIG. 5;
FIG. 5C is an enlarged cross-sectional view of the Clad 2, Multiple Clad 1 in FIG. 5;
FIG. SD is an enlarged cross-sectional view of the Multiple Draw and Anneal in FIG. 5;
FIG. SE is an enlarged cross-sectional view of the Clad 3, Multiple Clad 2 in FIG. 5;
FIG. SF is an enlarged cross-sectional view of the Multiple Draw and Anneal in FIG. 5;
FIG. 6 is a block diagram of a second method of producing a fiber tow for fabricating a second embodiment of the battery plate shown in FIGS. 3 and 4;
FIG. 6A is an enlarged cross-sectional view of the Clad 1, Single Wire in FIG.
6;
FIG. 6B is an enlarged cross-sectional view of the Multiple Draw and Anneal in FIG. 6;
Wo 95135177 ~ t ~ 9 9 ~ 4 PCT/U~g ~ 8 FIG. 6C is an enlarged cross-sectional view of the Additional Draw and Anneal in FIG. 6;
FIG. 6D is an enlarged cross-sectional view of the Clad 2, Multiple Clad 1 in FIG. 6;
FIG. 6E is an enlarged cross-sectional view of the Multiple Draw and Anneal in FIG. 6;
FIG. 6F is an enlarged cross-sectional view of the Clad 3, Multiple Clad 2 in FIG. 6;
FIG. 6G is an enlarged cross-sectional view of the Multiple Draw and Anneal in FIG. 6;
FIG. 7 is a block diagram of the method of making a web of metallic fibers;
FIG. 8 is a diagram of the process for separating and randomly orienting the metallic fibers to form a web; and FIG. 9 is a block diagram of the method of making the electric storage battery of FIG. 1.
Similar reference characters refer to similar parts throughout the several Figures of the drawings.
WO 95/3S177 ~ 9 5 ~ PCT/US95/07588 .
DETAILED DISCUSSION
FIG. 1 is an isometric view of an example of an electric storage battery 10 of the present invention. FIG. 2 illustrates the internal configuration of the electric storage battery 10 of FIG. 1. The electric storage battery l0 comprises an anode 11 and a cathode 12 with a sepa.~tor 13 interposed therebetween. The anode 11, the cathode 12 and the separator 13 are established in an adjacent relationship and rolled to form a cylindrical battery configuration. The anode 11 and the cathode 12 arerespectively connected to anode and cathode terminals 16 and 18 by conventional means (not shown) as should be well known in the art. The anode 11 comprises an anode plate 21 constructed of a porous material with an anode active material 31disposed in the pores of the anode plate 21. The cathode 12 comprises a cathode plate 22 constructed of a porous material with a cathode active material 32 disposed in the pores of the cathode plate 22. The anode active material 31 and the cathode active material 32 is commonly referred to as a battery paste. The anode plate 21 and the 15 cathode plate 22 are constructed of a conductive material for providing electrical conductivity between the anode active material 31 and the cathode active material 32 with the anode plate 21 and the cathode plate 22, respectively, as should be well known to those skilled in the art.
FIG. 3 is a m~gnified view of a portion of the improved battery plate 40 of the present invention comprising a plurality of metallic fibers 50. Each of the plurality of metallic fibers 50 is formed of a flexible and resilient solid metallic material for providing a flexible battery plate 21. The type of metallic material used for forming the battery plate 40 is selected by the type of battery to be constructed as well as the active material used and the polarity of the battery plate.
Each of the plurality of metallic fibers 50 has a substantially cylin-lric~l shape with a major diameter D and a substantially uniform length L. Preferably, each of the plurality of metallic fibers 50 has a length L at least one thousand times the major diameter D. As shown in FIG. 3, the plurality of metallic fibers 50 are substantially randomly oriented in multiple planes of the battery plate 40. Each of the plurality of metallic fibers 50 is fused to an adjacent one of the plurality of metallic fibers 50 for forming the conductive battery plate 40 with a multiplicity of pores 60 defined therein.
The plurality of met~llic fibers 50 are fused to adjacent metallic fibers 50 in the same WO 9S/35177 ~ t ~ PCTIUS95/07588 plane as well as adjacent planes of the multiple layer battery plate 40 to form a three ~imen~ional metallic fiber matrix having multiple layers of adjacent metallic fibers 50 with the multiplicity of pores 60 defined therein. Preferably, the plurality of metallic fibers 50 are fused to adjacent metallic fibers 50 by a sintering process.
S Optionally, the plurality of mPt~llic fibers 50 comprises a nli~ule of a plurality of major diameter metallic fibers 51 and a plurality of minor diameter metallic fibers 52. Each of the plurality of major metallic fibers 51 has a major diameter (D) and a substantially uniform length (L). Each of the plurality of minor metallic fibers 52 has a minor diameter (d) and a substantially uniform length (l). Preferably, the major In diameter metallic fibers 51 having a major diameter (D) at least twice the minor diameter (d) of each of the minor diameter fibers 52. The length L of each of the plurality of major metallic fibers 51 is equal to the length (1) of each of the plurality of minor diameter metallic fibers 52.
In one example of the invention, the plurality of major metallic fibers 51 and 15 the plurality of minor metallic fibers 52 are formed of a nickel metallic material. The plurality of major m~t~llic fibers 51 have a major diameter (D) of 4.0 microns and a substantially uniform length (L) of 2.54 centimeters. The plurality of minor metallic fibers 52 have a minor diameter (d) of 2.0 microns and a substantially unirollll length (I) of 2.54 ce~,~;r"eL~,~. The specific ratio of the plurality of major m.ot~llic fibers 51 20 to the plurality of rninor metallic fibers 52 may be determined by the desired porosity of the battery plate 40, the metallic materials used and the process for making the metallic fibers 50.
FIG. 4 is a m~gnified view similar to FIG. 3 illustrating the improved battery plate 40 of FIG. 3 with the active material 65 thereon. The active material 65 is 25 pressed into the pores 60 in the battery plate 40 in a conventional manner. The plurali-ty of metallic fibers 50 are resilient for resiliently interlocking the active plate material 65 into the multiplicity of pores 60 of the battery plate 40. In addition, the plurality of metallic fibers 50 resiliently interlock the active material 65 within the multiple layers of adjacent fibers 50.
The cylinrlric~l shape of adjacent metallic fibers 50 create generally wedge-shape regions which entrap the active material 65 for insuring that the active m~teri~l 65 is maintained in electrical conductivity with the battery plate 40 during vibration, wo95135177 ~ 5~ PCT/U~5~1~/5~8 shock and the like. It is further believed that during the pasting process, the resilient metallic fibers resiliently deform when the active material 65 is pressed within the battery plate 40 by an external pressure. The resilient deformation of the metallic fibers 50 produces a resilient bias which resiliently maintains the active material 65 within the battery plate 40. The resilient bias continues to maintain the active material 65 within the battery plate 40 as the active material 65 is depleted from the battery plate 40. As the active material 65is depleted from the battery plate 40, the resiliency bias of the metallic fibers 50 return the metallic fibers 50 toward a non-deformed condition which maintains the engagement of the metallic fibers 50 with the active material 65. The resiliency bias of the metallic fibers 50 insure that the active material 65 m~int~in~ in electrical conductivity with the battery plate 40 even after substantial depleion of the active material 65.
FIG. 5 is a block diagram of a first method of producing a fiber tow for fabricating a first embodiment of the battery plate shown in FIGS.3 and 4. The first method of making a fiber tow provides uniform rli~m~t~r metallic fibers from a metallic wire 1 10 through the use of a first, second and third cladding 111-113. The metallic wire 110 is selected to be resistant to a removal process such as being resistant to a selected acid or as being resistant to a selected electrolysis process.
FIG.5 illustrates a first cladding process 121 for cladding the metallic wire 110 with a cladding material 116 to provide the first cladding 111. The cladding material 116 is selected to be removable in a removal process such as being soluble in a selected acid or as being removable in a selected electrolysis process as will be described in greater detail hereinafter. Preferably, the cladding material 116is a strip of material that is bent to l-ilcu-nscribe the outer diameter 1 lOD of the metallic wire 110.
FIG. 5A is a cross-sectional view of the first cladding 111 having an outer diameter 11 lD. Preferably, the first cladding 111 is continuously passed through the annealing oven having an inert atmosphere.
FIG.5 illustrates a drawing and annealing process 122 of the first cladding 111.Preferably, the drawing and annealing process 122 of the first cladding 111 includes the successive drawing and ~nne~ling of the first cladding 111 for reducing the outer diameter l l lD.
Wo 95/35177 2 1 ~ ~ 9 5 ~ PCT/US95/07S88 FIG. 5B is a cross-sectional view of the first cladding 111 after passing through the drawing and annealing process 122.
FIG. 5 illustrates a second cladding process 123 for cladding a plurality of thefirst clafl-ling~ 111 with the cladding material 116 to provide the second cladding 112.
FIG. 5C is a cross-sectional view of the second cladding 112 illustrating a plurality of the first claddings 111 within the second cladding 112.
FIG. 5 illustrates a drawing and annealing process 124 of the second cladding 112. Preferably, the drawing and annealing process 124 of the second cladding 112 includes the successive drawing and annealing of the second cladding 112 for reducing the outer diameter 11 lD.
FIG. 5D is a cross-sectional view of the second cladding 112 after passing through the drawing and annealing process 124.
FIG. S illustrates a third cladding process 125 for cladding a plurality of the second claddings 112 with a cladding material 116 to provide the third cl~dding 113.
FIG. 5E is a cross-sectional view of the third cladding 113 illustrating a plurality of the second cla~-ling~ 112 within the third cladding 113.
FIG. 5 illustrates the drawing and annç~ling process 126 of the third cladding 113. Preferably, the drawing and anne~ling process 126 of the third cladding 113includes the successive drawing and annç~ling of the third cladding 113 for reducing the outer diameter 11 lD.
FIG. SF is a cross-sectional view of the third cladding 113 after passing through the drawing and annçaling process 126.
FIG. 6 is a block diagram of a second method of producing a fiber tow for fabricating a second embodiment of the b?ttery plate 40 shown in FIGS. 3 and 4. The second method of making a fiber tow provides major ~iamçter metallic fibers 141 and provides minor rliameter met~llic fibers 142 from a metallic wire 210 through the use of a first, second and third cladding 211-213.
FIG. 6A is a cross-sectional view of the first cladding 211 having an outer diameter 21 lD. Preferably, the first cladding 211 is continuously passed through the ~nnç~ling oven having an inert atmosphere.
FIG. 6 illustrates a drawing and annealing process 222 of the first cladding 211.
Preferably, the drawing and annç~ling process 222 of the first cladding 211 includes WO 95/35177 ~ ~ 6 9~ q 5 ~ PCT/US95/07588 the successive drawing and annealing of the first cladding 211 for reducing the outer diameter 21 lD.
After the first cladding 211 is passed through the drawing and annealing process222, the first cladding 211 is separated into a primary portion 241 and a secondary S portion 242. The secondary portion 242 of the first cladding 211 is passed through an additional draw and annealing process 222A for further reducing the outer rii~rneter 21 lD.
FIG. 6B is a cross-sectional view of the primary portion 241 of the first cladding 211 after passing through the drawing and ~nnçaling process 222. FIG. 6C
is a cross-sectional view of the secondary portion 242 of the first cladding 211 after passing through the additional drawing and ~nne~ling process 222A. The first cladding 211 in the primary portion 241 defines a major diameter whereas the first cladding 211 in the secondary portion 242 defines a minor (li~meter. The minor diameter of the secondary portion 242 of the first cladding 211 has a substantially smaller cross-sectional area relative to the major diameter of the primary portion 241 of the first cladding 211.
FIG. 6 illustrates a second cladding process 223 for cladding a plurality of theprimary portion 241 and a plurality of the secondary portions 242 of the first claddings 211 with a cladding material 216 to provide the second cladding 212.
FIG. 6D is a cross-sectional view of the second cladding 212 illustrating a plurality of the primary and secondary portions 241 and 242 of the first claddings 211 within the second cladding 212.
FIG. 6 illustrates a drawing and annealing process 24 of the second cladding 224. Preferably, the drawing and ~nne~ling process 224 of the second cladding 212 includes the successive drawing and ~nnç~ling of the second cladding 212 for reducing the outer rli~meter 211D.
FIG. 6E is a cross-sectional view of the second cladding 212 after passing through the drawing and annealing process 224.
FIG. 6 illustrates a third cladding process 225 for cladding a plurality of the second claddings 212 with a cladding material 216 to provide the third cladding 213.
FlG. 6F is a cross-sectional view of the third cladding 213 illustrating a plurality of the second claddings 212 within the third cladding 213.
WO 95/35177 PCr/uss5/07588 2~qq5~ ~
FIG. 6 illustrates a drawing and annealing process 226 of the third cladding 213.
Preferably, the drawing and annealing process 226 of the third cladding 213 includes the successive drawing and annç~ling of the third cladding 213 for reducing the outer diameter 21 lD.
FIG. 6G is a cross-sectional view of the third cladding 213 after passing through the drawing and annealing process 226.
FIG. 7 is a block diagram of the processing of the third cladding 213 to providea fiber tow 250 having the major diameter metallic fibers 141 and the minor ~ met--r metallic fibers 142. The third cladding 213 is passed through the severing device 271 I() for breaking the third cladding 213 into segment of a desired length. The severed segments of the third cladding 213 is subjected to the removing process 272 to remove the cladding material 216 to produce metallic fibers 270 of a desired length. The cladding removing process 272 may be a leaching process wherein the third cladding 213 is immersed into an acid for dissolving an acid soluble cladding material 216.
In the alternative, the removing process 272 may include an electrolysis process for removing the cladding m~t~ri~l 216.
The metallic fibers 260 comprises a plurality of major wire fibers 261 and a plurality of minor wire fibers 262. Each of the plurality of major wire fibers 261 has a major diameter whereas each of the plurality of minor wire fibers 262 has a minor ~ meter. The ratio of primary portion 241 to the secondary portion 242 in the second cladding 212 determines the ratio of the quantity of major wire fibers 261 to the quantity of the minor wire fibers 262.
After completion of the removing process 272, wire fibers 260 are separated or opened into individual loose metallic fibers 260. The individual loose metallic fibers 260 are subjected to an optional carder 274 for carding the wire fibers 260. Theoptional carder 274 bends each of the metallic fibers 260 to facilitate interconnection and interlinking when the metallic fibers 260 are formed into a web 280. The bends further facilitate the random orientation and substantially uniform distribution of the minor wire fibers 262 within the major wire fibers 261. The carded wire fibers 260 are formed into a web 280 by a weber 275.
FIG. 8 is a diagram of the process for separating and randomly orienting the met~llic fibers 260 to form a web 280. The substantially parallel metallic fibers 260 WO 95/35177 2 1 ~ ~ ~ 5 ~ PCTrUS95/07588 are placed in a hopper 300 and are conveyed by an inclined plane 302 to housing 304 containing a plurality of rollers 311-31~. The inclined plane 302 directs the m~t~llic fibers 260 to rotating opener rollers 311 and 312 for partially opening the metallic fibers 260. The partially opened metallic fibers 260 pass from the opposite rotating opener rollers 311 and 312 to the main opener cylinder 314. The rotating opener roller-313 returns excess metallic fibers 260 to the hopper 300. The partially opened metallic fibers 260 pass between the main opener cylinder 314 and a working roller 315 and a stripper roller 316 that cooperate with the main opener cylinder 314 for further opening and blending the metallic fibers 260. The opened and blended metallic fibers 0 260 are passed through an air roller 317 for subjecting the metallic fibers 260 to a high velocity air stream and for transferring the metallic fibers 260 through a conduit 318 to an air separator 320.
The air separator 320 further sep~tes and opens the metallic fibers 260 by high velocity air. The opened metallic fibers 260 settle onto a horizontal conveyor 321 and 15 are moved to an elevating conveyor 322. The metallic fibers 260 are passed between the elevating conveyor 322 and a ~ er conveyor 323 to return any excess of the opened metallic fibers 260 to the horizontal conveyor 321. The met~llic fibers 260 passing between the elevating conveyor 322 and the ~LIipp~l conveyor 323 are project-ed by the elevating conveyor 322 to a first condenser screen 325 and a plurality of 20 roller conveyors 326.
The first condenser screen 325 is provided with an air flow by a blower 330 througlh a suction duct 331 as in~lic~ted by the arrows. The air pressure above the first condenser screen 325 iS below atmospheric l~r~s~u.~ and accordingly the air flow passes through the first condenser screen 325 into the suction duct 331 as indicated by the 25 arrows to determine the quantity of the metallic fibers 260 attracted to the first condenser screen 325. As the metallic fibers 260 acc--mul~te on the first condenser screen 325, the air flow passing through the first condenser screen 325 iS proportionally reduced until an equilibrium is reached and a continuous and uniform mat of metallic fibers 332 are disposed upon the first condenser screen 325.
The uniform mat of metallic fibers 332 is moved over a feed plate 335 by feed rollers 336 to a lickerin 340. The uniform mat of metallic fibers 341 are combed by the lickerin 340 for producing individual met~llic fibers 260A. The individual metallic WO95135177 21 ~9~ PCTnJ~g~1~7588 ~
fibers 260A are directed by an air stream provided by a blower 341 and a pressure duct 342 to a second condenser screen 345. The velocity of the air stream generated by the blower 341 is controlled by an opening belwæll the lickerin 340 and a saber 346.
The saber 346 is mounted on an eccenL~ ic (not shown) for varying the opening between S the lickerin 340 and a saber 346 to control the air flow therethrough.
As the metallic fibers 260A accllm~ te on the second condenser screen 345, the air flow passing through the second condenser screen 345 is proportionally reduced until an equilibrium is reached and a continuous and uniform web of met~llic fibers 280 is disposed upon the second condenser screen 345. The uniform web of metallic fibers 280 is directed to an output conveyor 348 for completing the process of making the web 280.
FIG. 9 is a block diagram of the method of making the electric storage battery of FIG. 1. The web 280 is subjected to a sintering process 351 for fusing the metallic fibers 260 within the web 280. The web 280 subjected to a process 352 to form the battery plate 40. The battery plate 40 is passed through a pasting process 353 for adding the active material 65 to the battery plate 40. The pasted battery plate 40 is then processed through a final assembly 354 for adding the anode and cathode termi-nals 16 and 18.
The improved battery plate of the present invention has a number of advantages 20 over the battery plates of the prior art. Typically, the fibers forming the battery plate are normally 12 to 25 millimeters long with a ~ meter of 1.0 micron to 30.0 microns.
The metallic fibers are extremely strong and bend when the battery plate is rolled into a cylindrical configuration without any loss of conductivity of the metallic fibers.
Accordingly, each of the metallic fibers is assured electrical conductivity for a dimen-25 sion of 12 to 25 millimeters. In contrast, the battery plates of the prior art made of powdered materials is only assured electrical conductivity across the tli~met~or of the powdered particle. Although each of the metallic fibers has a relatively large linear dimension, it has a very small rli~meter dimension compared to metallic formed plates of the prior art. Accordingly, the electrical conductivity between the active material 30 and the battery plate in the present invention is much shorter in distance than the prior art metallic battery plates. Furthermore, as can be seen in Fig. 3, the metallic fibers ~WO 95/35177 2 1 ~ 5 4 PCTIUS95/07S88 form multiple layers in the matrix to further reduce the short distance between the active material and the battery plate.
Another advantage of the present invention is the maximum contact between adjacent metallic fibers at points along the respective length of each of the fibers in S the sintering process. Each of the metallic fibers has a cylindrical to cylinder contact with adjacent fibers which can be carefully controlled in the sintering oven to insure a proper fusing of the materials. The cylindrical to cylinder contact insures a high electrical conductivity between adjacent metallic fibers while allowing the improved battery plate to flex and bend for use in large variety of battery configurations.
A further advantage of the present invention is the multiple layers of the cylindrical fibers entrapping the active material therein. Adjacent cylindrical fibers form wedge-shape regions which entrap the active material therein for insuring that the active material is maintained in electrical conductivity with the battery plate through vibration, shock and the like. It is further believed that during the pasting process, the metallic fibers resiliently bend to accommodate for the active material when the active material is forced within the battery plate by an active ~les~ulc. This flexing of the metallic fibers produces a resiliency which resiliently holds the active material within the improved battery plate. Furthermore, it is further believed that as the active material is depleted from the battery plate, the resiliency of the metallic fibers urge the metallic fibers to the undistorted position which maintains the engage-ment with the active material to insure that the active material maintains the electrical conductivity with the battery plate even when the active material is substantially depleted. A battery plate 40 having a porosity of 95% to 98% is possible through the use of the present invention.
Table I illustrates the physical and electrical characteristics of four prior art battery plates used commercially in the art. The Celmet battery plate is constructed of a nickel foam material in accordance with the teaching of U.S. patents 4,251,603.
The Nihon Seison and Katayama battery plates are constructed of a nickel coated plastic material.
The specifications set forth in Table I are either the specifications of the manufacturers or are measured p~ ln(,LCIS. The resi~t~nce values set forth in Tables I and II were measured between two positions 10.0 ce..Lh--elels apart on a strip of WO95135177 2 1 6 9 9 5 ~ PCT/US95/07588 battery plate 1.0 centimeters wide and 12.0 centimet~rs in length. The ABS value of the pore size distribution indicates the maximum limiting pore di~mPter or the maxi-mum diameter of a particle that can pass through the battery plate. The percentage of the pore size distnbution 5 was determined by a wet flow test. The ~ entage of the pore size distribution indicates the pore size at which that percentage of flow is passing through pores of the indicated diameter or smaller.
The value for the ABS was determined by a wet bubble point test whereas the values for the 98%, 90% and 50% pore size distribution were statistically determined 10 by a combination of the wet bubble point test and a dry air flow test. The values of Tables I and II are believed to accurately refiect the true porosity and to provide a true companson of porosity values for the battery plates.
TABLE I
CHARACTERISTICS PRIOR ART BATTERY PLATES
MEDIA CELMET NIHON SEISON KATAYAMA
Porosity (%) 94.5 90.0 94.0 Base Weight (o%/yd2) 16.2 12.5 12.7 Thickness (mm) 1.5 1.0 1.2 Tensile Strength (psi) 170 120 168 Recic~ re (mS2) 39 80 83 Resistivity (mQ) 0.69 0.80 0.83 Pore Si%e Distribution (,um) AsS 265 180 215 98% 265 145 155 90% 260 125 125 50% 185 80 75 Table II illustrates the physical and electrical characteristics of the first embodi-ment of the improved battery plate 40 of the present invention. The eight types of specimens of the improved battery plate 40 were all made from 25 micron nickel fiber.
WO95/3S177 2 1 ~ ~ ~ 5 4 PCT~S95/07588 .
TABLE II
~CKEL ~BER BATTERY PLATE(25um) Porosity(%) 95% 95% 95.5 95.5 96.0 96.0 96.5 96.5 Base Weight (o~yd2) 13.5 17.5 13.5 17.5 13.5 17.5 13.5 17.5 Thic~ess (mm) 1,0 1.3 1 1 15 13 17 1 5 19 Tensile S~eng~ (psi) 230 230 210 210 180 180 165 165 Resis~nce (mn) 55 40 55 40 55 40 55 40 Res~vity (m~-cm) 0.75 0.47 0.83 0.54 0.98 0.61 1.13 0.69 Pore Size Distribution (~
98% 200 200 210 210 230 230 250 250 90~ 190 190 190 190 210 210 240 240 50% 125 125 125 125 135 135 160 185 A comparison of Table I and Table II reveals the superior performance of the improved battery plate 40 over the battery plates of the prior art. The improved battery plate 40 has superior resistivity, porosity and tensile strength over the battery plates of the prior art.
Typically, the volume of the battery plate is measured by a liquid displacement 20 process for determining the porosity of the battery plate. It should be realized that the porosity of the improved battery plate 40 is an accurate porosity since the metallic fibers 260 are solid fibers. In many cases, the stated porosity of the powdered or plated plastic battery plates of the prior art are inaccurate since the powdered or plated plastic materials have internal voids or filler materials of dir~c;nt densities that are 25 inc~p~hle of recelving active material. The porosities of Table I are based on estim~tes of the determined porosity values as set forth above. Accordingly, the performance - of the improved battery plate 40 over the battery plates of the prior art is believed to be as indicated in Tables I and II.
The present disclosure includes that contained in the appended claims as well 30 as that of the foregoing description. Although this invention has been described in its WO 95/3Sl77 2 1 6 ~ ~ 5 4 PCT/USg5/07588 ~
preferred form with a certain degree of particularity, it is understood that the present disclosure of the pre~l.ed forrn has been made only by way of example and that numerous changes in the details of construction and the combination and arrangement of parts may be resorted to without departing from the spirit and scope of the inven-5 tion.
Claims (30)
1. The method of making a battery plate for an electric storage battery, comprising the steps of:
forming a tow of metallic fibers;
severing the tow of metallic fibers to provide metallic fibers;
forming the metallic fibers into a web; and fusing the metallic fibers within the web to form a battery plate.
forming a tow of metallic fibers;
severing the tow of metallic fibers to provide metallic fibers;
forming the metallic fibers into a web; and fusing the metallic fibers within the web to form a battery plate.
2. The method of making a battery plate as set forth in claim 1, wherein the step of forming a tow of metallic fibers includes cladding and drawing a plurality of metallic wires for providing a drawn cladding with a reduced diameter; and removing the cladding to provide the fiber tow.
3. The method of making a battery plate as set forth in claim 1, wherein the step of forming a tow of metallic fibers includes forming each of the metallic fibers to have a substantially cylindrical shape.
4. The method of making a battery plate as set forth in claim 1, wherein the step of forming a tow of metallic fibers includes forming the tow of metallic fibers with each of the metallic fibers having a substantially cylindrical shape with a diame-ter; and severing the tow of metallic fibers to provide metallic fibers having a length at least one thousand times the diameter.
5. The method of making a battery plate as set forth in claim 1, wherein the step of forming a tow of metallic fibers includes forming the tow of metallic fibers with each of the metallic fibers having a substantially cylindrical shape; and forming a portion of the tow of metallic fibers to have a major diameter and forming a portion of the tow of metallic fibers to have a minor diameter to form a battery plate with major and minor diameter metallic fibers.
6. The method of making a battery plate as set forth in claim 1, wherein the step of forming a tow of metallic fibers includes forming the tow of metallic fibers with each of the metallic fibers having a substantially cylindrical shape;
forming a portion of the tow of metallic fibers to have a major diameter and forming a portion of the tow of metallic fibers to have a minor diameter; and randomly orienting the metallic fibers having the minor diameter to be substantially uniformly distributed within the metallic fibers having the major diameter within the web.
forming a portion of the tow of metallic fibers to have a major diameter and forming a portion of the tow of metallic fibers to have a minor diameter; and randomly orienting the metallic fibers having the minor diameter to be substantially uniformly distributed within the metallic fibers having the major diameter within the web.
7. The method of making a battery plate as set forth in claim 1, wherein the step of forming a tow of metallic fibers includes forming the tow of metallic fibers with each of the metallic fibers having a substantially cylindrical shape;
forming a portion of the tow of metallic fibers to have a major diameter and forming a portion of the tow of metallic fibers to have a minor diameter with the major diameter being at least twice the minor diameter; and severing the tow of metallic fibers to provide metallic fibers having a length at least one thousand times the major diameter.
forming a portion of the tow of metallic fibers to have a major diameter and forming a portion of the tow of metallic fibers to have a minor diameter with the major diameter being at least twice the minor diameter; and severing the tow of metallic fibers to provide metallic fibers having a length at least one thousand times the major diameter.
8. The method of making a battery plate as set forth in claim 1, wherein the step of fusing the metallic fibers within the web includes sintering the web for fusing adjacent fibers to provide an electrically conductive battery plate having a multiplicity of pores therein.
9. The method of making a battery plate as set forth in claim 1, wherein the step of fusing the metallic fibers within the web includes sintering the web for fusing adjacent fibers to provide multiple conductive planes with each of the conductive planes having a multiplicity of pores defined between adjacent fibers for receiving an active material therein.
10. The method of making a battery plate for an electric storage battery, comprising the steps of:
cladding a metallic wire with a cladding material to provide a first cladding;
drawing a primary portion of the first cladding for reducing the diameter thereof to have a major diameter;
drawing a secondary portion of the first cladding for reducing the diameter thereof to have a minor diameter;
cladding a plurality of the primary and the secondary portions of the first drawn claddings to provide a second cladding;
drawing the second cladding for reducing the diameter thereof;
removing the cladding material to provide a fiber tow comprising metallic wires having the major diameter and metallic fibers having the minor diameter;
severing the fiber tow into uniform length to provide metallic fibers;
forming the metallic fibers into a web; and sintering the web to form a battery plate.
cladding a metallic wire with a cladding material to provide a first cladding;
drawing a primary portion of the first cladding for reducing the diameter thereof to have a major diameter;
drawing a secondary portion of the first cladding for reducing the diameter thereof to have a minor diameter;
cladding a plurality of the primary and the secondary portions of the first drawn claddings to provide a second cladding;
drawing the second cladding for reducing the diameter thereof;
removing the cladding material to provide a fiber tow comprising metallic wires having the major diameter and metallic fibers having the minor diameter;
severing the fiber tow into uniform length to provide metallic fibers;
forming the metallic fibers into a web; and sintering the web to form a battery plate.
11. The method of making a battery plate as set forth in claim 10, wherein the step of forming a tow of metallic fibers includes forming each of the metallic fibers to have a substantially cylindrical shape.
12. The method of making a battery plate as set forth in claim 10, wherein the step severing the tow of metallic fibers includes severing the fiber tow to provide metallic fibers having a length at least one thousand times the major diameter.
13. The method of making a battery plate as set forth in claim 10, wherein the step of forming the metallic fibers into a web includes randomly orienting the metallic fibers into a matrix within the web.
14. The method of making a battery plate as set forth in claim 10, wherein the step of sintering the metallic fibers within the web includes sintering the web for fusing adjacent fibers to provide an electrically conductive battery plate with a multi-plicity of pores defined between adjacent fibers for receiving an active material therein;
and pasting an active material within the multiplicity of pores defined between adjacent fibers of the web.
and pasting an active material within the multiplicity of pores defined between adjacent fibers of the web.
15. An improved battery plate for an electric storage battery, comprising:
a plurality of metallic fibers;
said plurality of metallic fibers being substantially randomly oriented in a web; and each of said plurality of metallic fibers being fused to an adjacent one of said plurality of metallic fibers for forming a conductive battery plate with a multiplicity of pores defined therein.
a plurality of metallic fibers;
said plurality of metallic fibers being substantially randomly oriented in a web; and each of said plurality of metallic fibers being fused to an adjacent one of said plurality of metallic fibers for forming a conductive battery plate with a multiplicity of pores defined therein.
16. An improved battery plate for an electric storage battery as set forth in claim 15, wherein each of said plurality of metallic fibers has a substantially cylindrical shape with a major diameter; and each of said plurality of metallic fibers having a length at least one thousand times the major diameter.
17. An improved battery plate for an electric storage battery as set forth in claim 15, wherein said plurality of metallic fibers comprises a plurality of major diameter metallic fibers and a plurality of minor diameter metallic fibers; and each of said major diameter metallic fibers having a diameter at least twice the diameter of each of said minor diameter fibers.
18. An improved battery plate for an electric storage battery as set forth in claim 15, wherein said plurality of metallic fibers being substantially randomly oriented in said web includes said plurality of metallic fibers being substantially randomly oriented in multiple planes.
19. An improved battery plate for an electric storage battery as set forth in claim 15, wherein each of said plurality of metallic fibers is fused to an adjacent one of said plurality of metallic fibers by sintering said web.
20. An improved battery plate for an electric storage battery as set forth in claim 15, wherein each of said plurality of metallic fibers is flexible for providing a flexible battery plate.
21. An improved battery plate for an electric storage battery as set forth in claim 15, wherein each of said plurality of metallic fibers is resilient for resiliently interlocking an active plate material into said multiplicity of pores of said battery plate.
22. An improved battery plate for an electric storage battery as set forth in claim 15, wherein each of said plurality of metallic fibers being fused to an adjacent one of said plurality of metallic fibers for forming a conductive battery plate having multiple layers of adjacent fibers with a multiplicity of pores defined therein; and each of said plurality of metallic fibers being resilient for resiliently interlocking the active material within said multiple layers of adjacent fibers.
23. An improved battery plate for an electric storage battery as set forth in claim 15, wherein each of said plurality of metallic fibers comprises nickel metallic fibers.
24. An improved battery plate for an electric storage battery, comprising:
a mixture of a plurality of major diameter metallic fibers and a plurality of minor diameter metallic fibers;
said mixture of said plurality of minor diameter metallic fibers being randomly oriented and uniformly dispersed within said plurality of major diameter metallic fibers for defining a multiplicity of pores therebetween; and said mixture of plurality of major diameter metallic fibers being fused to said plurality of minor diameter metallic fibers for forming a conductive battery plate with said multiplicity of pores receiving a battery plate active material therein.
a mixture of a plurality of major diameter metallic fibers and a plurality of minor diameter metallic fibers;
said mixture of said plurality of minor diameter metallic fibers being randomly oriented and uniformly dispersed within said plurality of major diameter metallic fibers for defining a multiplicity of pores therebetween; and said mixture of plurality of major diameter metallic fibers being fused to said plurality of minor diameter metallic fibers for forming a conductive battery plate with said multiplicity of pores receiving a battery plate active material therein.
25. An improved battery plate for an electric storage battery as set forth in claim 24, wherein each of said plurality of metallic fibers has a substantially cylindrical shape with a major diameter; and each of said plurality of major diameter metallic fibers having a length at least one thousand times the major diameter.
26. An improved battery plate for an electric storage battery as set forth in claim 24, wherein each of said plurality of metallic fibers has a substantially cylindrical shape with a major diameter;
each of said major diameter metallic fibers having a diameter at least twice the diameter of each of said minor diameter fibers; and each of said plurality of major diameter metallic fibers having a length at least one thousand times the major diameter.
each of said major diameter metallic fibers having a diameter at least twice the diameter of each of said minor diameter fibers; and each of said plurality of major diameter metallic fibers having a length at least one thousand times the major diameter.
27. An improved battery plate for an electric storage battery as set forth in claim 24, wherein each of said plurality of metallic fibers is flexible for providing a flexible battery plate.
28. An improved battery plate for an electric storage battery as set forth in claim 24, wherein each of said plurality of metallic fibers is resilient for resiliently interlocking an active plate material into said multiplicity of pores of said battery plate.
29. An improved battery plate for an electric storage battery as set forth in claim 24, wherein each of said plurality of metallic fibers comprises nickel metallic fibers.
30. An improved electric storage battery, comprising:
an anode plate comprising a sintered mixture of a plurality of major diameter metallic fibers and a plurality of minor diameter metallic fibers forming a conductive plate with a multiplicity of pores defined therein;
each of said plurality of metallic fibers being resilient for resiliently interlocking an anode plate material into said multiplicity of pores defined within said anode plate;
a cathode comprising a sintered mixture of a plurality of major diameter metallic fibers and a plurality of minor diameter metallic fibers forming a porous conductive member;
each of said plurality of metallic fibers being resilient for resiliently interlocking a cathode plate material into said multiplicity of pores defined within said cathode plate; and each of said plurality of metallic fibers being flexible for providing a flexible anode and cathode.
an anode plate comprising a sintered mixture of a plurality of major diameter metallic fibers and a plurality of minor diameter metallic fibers forming a conductive plate with a multiplicity of pores defined therein;
each of said plurality of metallic fibers being resilient for resiliently interlocking an anode plate material into said multiplicity of pores defined within said anode plate;
a cathode comprising a sintered mixture of a plurality of major diameter metallic fibers and a plurality of minor diameter metallic fibers forming a porous conductive member;
each of said plurality of metallic fibers being resilient for resiliently interlocking a cathode plate material into said multiplicity of pores defined within said cathode plate; and each of said plurality of metallic fibers being flexible for providing a flexible anode and cathode.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/263,542 US5584109A (en) | 1994-06-22 | 1994-06-22 | Method of making a battery plate |
US08/263,542 | 1994-06-22 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2169954A1 true CA2169954A1 (en) | 1995-12-28 |
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ID=23002186
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA 2169954 Abandoned CA2169954A1 (en) | 1994-06-22 | 1995-06-20 | Improved battery plate and method of making |
Country Status (7)
Country | Link |
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US (1) | US5584109A (en) |
EP (1) | EP0725699A1 (en) |
JP (1) | JPH09504905A (en) |
CN (1) | CN1131922A (en) |
AU (1) | AU683396B2 (en) |
CA (1) | CA2169954A1 (en) |
WO (1) | WO1995035177A1 (en) |
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-
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-
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- 1995-06-20 AU AU28295/95A patent/AU683396B2/en not_active Ceased
- 1995-06-20 EP EP19950923878 patent/EP0725699A1/en not_active Withdrawn
- 1995-06-20 WO PCT/US1995/007588 patent/WO1995035177A1/en not_active Application Discontinuation
- 1995-06-20 JP JP50246496A patent/JPH09504905A/en active Pending
- 1995-06-20 CA CA 2169954 patent/CA2169954A1/en not_active Abandoned
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JPH09504905A (en) | 1997-05-13 |
CN1131922A (en) | 1996-09-25 |
AU683396B2 (en) | 1997-11-06 |
EP0725699A1 (en) | 1996-08-14 |
AU2829595A (en) | 1996-01-15 |
US5584109A (en) | 1996-12-17 |
WO1995035177A1 (en) | 1995-12-28 |
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