CA1073044A - Separator for secondary alkaline batteries - Google Patents

Separator for secondary alkaline batteries

Info

Publication number
CA1073044A
CA1073044A CA283,581A CA283581A CA1073044A CA 1073044 A CA1073044 A CA 1073044A CA 283581 A CA283581 A CA 283581A CA 1073044 A CA1073044 A CA 1073044A
Authority
CA
Canada
Prior art keywords
titanate
weight
matrix
present
forming material
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.)
Expired
Application number
CA283,581A
Other languages
French (fr)
Inventor
Roland F. Chireau
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yardney Electric Corp
Original Assignee
Yardney Electric Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Yardney Electric Corp filed Critical Yardney Electric Corp
Application granted granted Critical
Publication of CA1073044A publication Critical patent/CA1073044A/en
Expired legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/44—Fibrous material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H01M50/434—Ceramics
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • H01M2300/0014—Alkaline electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Cell Separators (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

Abstract of the Disclosure A negative interseparator for use as a component in a separator system for alkaline rechargeable batteries comprises about 50% to 95% by weight of a titanate material such as potassium titanate, a matrix-forming fibrous material, and a thickening agent for use in forming the interseparator. The negative interseparator is interposed between the negative electrode and "main separator" in the aforementioned batteries.

Description

~ 1073044 This invention relates to secondary alkaline batteries and, more particularly, it relates to separator systems for use in such batteries.
As described, for example, in Falk and Salkind, Alkaline Stora~e Batteries, pp. 168-170 (1969), it is well known that it is advantageous to interpose a separator system between the electrodes of opposite polarity in rechargeable alkaline batteries, such as silver/zinc and nickel/zinc batteries. In general, such separator systems include materials which are permeable to the electrolyte, but which reduce the migration of ionic or molecular species from one electrode to the other and retard, if not inhibit, dendritic growth from one electrode to~ard another.
The separator system may include a single separator made up of one or more layers of a semi-permeable membrane made from, for example, CELLOPHANE ~a film produced from wood pulp by the viscose process), polyethylene or polypropylene. More commonly, a separator system will comprise (a) A main separator-which is a semi-permeable membrane as described, together with (b) A spacer or "positive interseparator" forming a macro-porous barrier between the oxidizing ~+) electrode and the main separator and (c) A spacer or "negative interseparator" positioned between the reducing (-) electrode and the main separator.
The material forming the positive interseparator is usually an inert base polymer such as nylon, polypropylene, or a vinyl chloride/acrylonitrile copolymer (DYNEL ), whereas the negative interseparator may be formed from a cellulosic material, nylon or non-woven fabrics.
The negative interseparator serves, or at least is intended to serve, several functions in a cell. It imparts mechanical strength to an electrode, particularly when that * Trade Mark ' ~073044 1 electrode is composed largely of a powder, such as zinc oxide.
Additionally, it maintains non-adherent insoluble oxides ~which may be formed at the negative electrode during charge/discharge cycling) in direct contact with the negative electrode during the charging process so that the required electron transfer can occur. Another function of the negative interseparator is to maintain electrolytic contact across tne face of the electrode, whicn it can do by acting as a wick. The negative interseparator should also inhibit dendxitic growth from the negative electrode.
In batteries containing, for example, silver/zinc or nickel/zinc cells together wi~h the described separator systems and materials, it has been found that dendrites of metallic zinc grow from the zinc electrode into, and eventually across, the separator material after numerous charge/discharge cycles.
This dendritic growth causes the cells to short circuit.
Additionally, it has been found that after cycling, the negative interseparator becomes plated with zinc metal and penetrated by zinc particles. In that condition, it is not capable of per-forming its inten~ed function.
Although presently-available negative interseparators provide an advantage in alkaline rechargeable cells over their non-use, ion migration, dendritic growth, and current density non-uniformity still remain significant problems.

.
SUMMARY OF THE INVENTION
The herein-described invention is embodied in a negative interseparator for use in separator systems in rechargeable alkaline batteries. The negative interseparator comprises about 50% to about 95~ by weiglit of an inorganic titanate compound such as potassium titanate together with an inorganic fibrous material (other than the titanate~ and, preferably, a
-2-1 thickening agent to aid in producing the interseparators.
In those electrochemical alkaline cells in which migration of ions produced from the active negative electrode material and/or in which dendritic growth from the negative electrode toward the positive electrode is a problem, the herein-described negative interseparator effectively reduces such ion migration and dendritic growth as compared with negative inter-separators utilized heretofore. Additionally, this negative inter-separator can be used to advantage with all rechargeable alkaline cells because it absorbs and tenaciously retains electrolyte sO
that it effectively reduces electrolyte transport thereby minimizing exchange current density, while wetting the entire electrode surface exposed to electrolyte to ensure substantially uniform current density distribution over the wetted area and thereby minimizing electrode shape change. The herein-described negative intarseparator is also stable to the alkaline electrolyte and serves to mechanically strengthen the negative electrode.
-DESCRIPTION OF THE PREFERRED EMBODIMENT
The herein-described negative interseparator is an essentially inorganic, fibrous composite or admixt~i~e w~ich comprise~: ~a) ~n inorganic titanate, (b) An inorganic, fibrous material (other than the titanate) and, pre~erably (c) A
thickening agent. The interseparator is made from an admixture of the aforementioned components dispersed in a fluid medium.
Component (a~, i.e., the titanate,is the principal or "active" material in the interseparator in that it is primarily responsible for the improvements produced by the herein-described interseparator. The titanate may be, for example, potassium titanate, sodium titanate, magnesium titanate, calcium titanate, cerLum titanate, barium titanate, complex titanates such as , .................... .

1 magnesium-calcium titanate, and mixtures of the foregoing titanates. These titanates are usually fibrous themselves. A
typical size of presently-available potassium titanates is 0.2 microns in diameter x 10 microns in length.
Although the titanates are themselves fibrous, they are either too short and/or too brittle to be formed into a wovenlike structure. Therefore, it is necessary that a fibrous material of substantially greater length and flexibility than the presently-available titanate materials be incorporated in the interseparator in order to provide a matrix to mechanically bind together the titanate material. Any such fibrous material should, of coursa, be as inert to the alkaline media utilized in rechargeable alkaline batteries as possible so that the useful life of any such batteries in not materially reduced. Useful examples of such fibrous materials include chrysotile asbestos, zirconia fibers r alumino-silicate fibers and alumina fibers. Such fibers typically have length of 200 - 500 microns.
~ he fluid medium may be any liquid in which the other ~ components can be effectively dispersed and which does not adversely affect the electrochemical characteristics of the interseparator. Useful liquids include water and organic fluids such as lower molecular weight alcohols, e.g., isopropyl alcohol, butyl alcohol, and d~natured èthyl alcohol.
Because the viscosity of the fluid media in which components (a) and (b) are dispersed may be too low to prevent those components from separating from each other and~or agglomerating in portions of the liquid media, it is necessary in such cases to increase the viscosity of the fluid media to avoid the aforementioned separation problems to thereby maintain the components in substantially uniform dispersion in the fluid media. This can be accomplished in either of two ways.

.

1 First, a thic~ening agent, per se, can be added to the fluid media to increase the viscosity of the latter. The thickening agent may be a material which is soluble in the fluia media, but solubility is not required. In fact, it has been found that thickening agents which are swellable by a fluid medium to form colloidal gels may be utilized.
The thickening agent may function as a chemical binding agent;
J~ù~ illa~
however, this ~u~oiton--is anciallary to its primary fuction of increasing the fluid media viscosity. The thickening agent utilized herein should not functio~ as a film former since the resulting interseparator will then not exhibit the required microporous characteristics. Accoraingly, the term "thickening agent", as used herein, specifically excludes film-forming compounds.
Useful thickening agents are well known and include organic compounds, e.i., hydroxyethyl cellulose, ethyl cellulose, methyl cellulose, and sodium carboxymethyl cellulose, as well as inorganic compounds, e.g., sodium silicate. A useful organic thickening agent/organlc liquid medium combination i~ a 2% ~by wt:) solution of hydroxyethyl cellulose power in q5% ~by vol.) denatured ethyl alcohol.~ An inorganic thickening agent such as sodium silicate may be dissolved in water. Regardless of the thickening agent utilized, it should be one which is relatively - inert to the alkaline electrclytes encountered in alkaline rechargeable batteries so that the performance of such batteries is not materially decreased.
A second technique for increasing the viscosity of the liquid media involves use of part of the fibrous matrix material (or similar material) in comminuted form so that gels are formed with the liquid media. When using a matrix material such as the aforementioned asbestos, some of the latter may be reduced in .

1 size by mechanical means, e.g., a Waring blender, to produce su~-micron particles exhibiting colloidal properties. The comminution of the matrix-forming material may take place during the dispersion of the latter in the fluid medium. Sufficient matrix-forming material is comminuted to produc~ the required increase in the viscosity of the fluid medium, but sufficient matrix-forming material is left in its initial form to provide the matrix-forming functioni.
The amount of titanate may vary between about 50% and about 95~ by wèight of the weight of the herein-described components of the interseparator laminate (hereinafter abbreviated to "% by weigh~"). Below about 50~ by weight of the titanate material, the electrochemical properties of the interseparator are a`dversely affected for the reason that the latter begin to lose the characteristics impaited to them by the titanate and begin to acquire tho-~e characteristics (and limitations) imparted to them by the fibrous matrix material'. For example, when utilizing a fibrous matrix m~terial such as asbestos, the latter is subject to attacX by the alkaline media with resultant break-down of the composite structure. On the other hand, fibrousmaterials which are not readily attacked by the alkaline media are generally hydrophobic and, therefore, do not provide sufficient absorption of electrolyte. Above 95% by weight of titanate material, the latter is in9ufficiently bound together. Pre~erably, the titanate is used in a weight range between about 75~ and about 92%. Within such range a good balance is provided between having sufficient titanate present to inhibit dendritic growth and negative electrode ion migration, etc., on the other hand, and having sufficient matrix material to provide a mechanically strong interseparator, on tne other hand.
TIle matrix material and thickening agent (if separate . .

10730~4 1 from the matrix material) are present in an amount sufficient to make up 100% by weight. Generally, the thickening agent is utilized in amounts between about 0.5% and about 5% by weight, although about 0.5% to about 2.5% by weight is prPferred.
The preferred range for the matrix-forming material is about 8% to 25% by waight, although it may be used in amounts between about 5% and about 50% by weight if no separate thickening agent is present and about 4.5% to 45% by weight if a separate thicken_ ing agent i5 present.
The negative interseparator may be made as follows using water as the fluid medium. An aqueous slurry is made up of components (a), (b) and (c) in the desired proportions within the concentration ranges previously described. Typically, the weight ratio of components (a), (b) and (c) to the water in the slurry is between about 0.02:1 and about ~.2:1 although ratios outside this range can be used depending upon the particular materials and amounts of components (a~, (b) and (c) used in a particular application. This aqueous slurry is placed on a moving belt and is moved past a doctor blade where the particulate materials are spread out to make a relatively uniformly thick slurry. Because of the presence of the thickening agent which functions to provide body to the slurry, the slurry constituents are maintained relatively uniformly distributed throughout the slurry and the latter is capable of holding a given thickness.
The slurry is next passed through à heating zone where it is preferably heated at a temperature of about 90C. to 100C.
until it is dried. The resulting mat is calendered to a final desired sheet thicknass, for example, 5-6 mils.
Formation of a negative interseparator utilizing an organic solvent rather than water is substantially the same as described when using a water-based slurry except that somewhat - ' different temperatures may be employed in the drying operation.
~ he negative interseparator is a microporous structure exhibiting minimum resistance to the flow of electrolyte. Such interseparators, when made from potassium titanate, asbestos and 2% thickening agent, typically have an average pore diameter on the order of 800 to 1200 microns and typically have a volume porosity on the order of 60 percent.
The described interseparator may be used together with a main separator or with a main separator and a positive inter-separator as is well known. ~ypically, the negative inter-separator is used as a "U"-wrap around the negative electrode.
One or more layers of the negative interseparator composite may be used together.
The alkaline cells in which the herein-described separator finds utility include silver/zinc, silver/cadmium, nickel cadmium, nickel/zinc, nickel/iron, mercuric oxide/ zinc, and mercuric oxide/cadmium cells. Such cells may contain sodium hydraxide, potassium hydroxide, lithium hydroxide, barium hydroxide, and combinations thereof, as the electrolyte, as is well known.

The invention will be further described by the follow-ing Example.

.

Silver zinc cells were constructed with each cell including two silver positive electrodes (measuring 1.62 in. x 1.5 inc. x 0.034 in.) and three zinc negative electrodes (measuring 1.62 in. x 1.5 in. x 0.042 in.) with the zinc electrodes being disposed on each side of the silver electrodes. The negative electrodes consisted of 95% by weight zinc oxide and 5~ by weight mercuric OXl de.
A separator system was employed in each cell utilizing the "U" wrap technique with each separator system comprising: a positive nylon (PELLON )interseparator; a silverized CELLOPHANE
main separator; and a negative interseparator comprising 89% by weight potassium titanate; 9% by weight chrysotile asbestos fiber, and 2% by weight carboxymethyl cellulose.
The aforementioned structure was disposed within a plastic casing to which thexe was added an aqueous potassium hydroxide solution comprising 40% by weight potassium hydroxide.
Each cell had the aforementioned structure and differad only in that different thicknesses of the negative interseparator were utilized as shown in the Table and with the further exception that one cell included a 5 mil thick ~ELLON interseparator in place of the negative titanate-containing interseparator.
Each of the cells was cycled on a 100~ depth of dis-charge level with a charging procedure consisting of overcharging the cells by 50% on each cycle. The data derived from such tests are shown in the Table.

TABLE
.

Ne~. Interseparator Cycles to 50~ of Cycles Or ginal Capaci~y to Short Type Thick.(mils) Titanate 6.5 105 120 do. 13 113 115 do. 20 98 105 As will be seen from the Table, the presence of a titanate-containing negative interseparator provides a substantial advantage over cells which do not contain such an interseparator.
Trade Mark _9_ '.

.
:

~073~44 1 It will also be noted from the Table that thickness of the titanate interseparator appears to have little effect on the working life of a cell.

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.

~ .
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.

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Claims (17)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
1. In a rechargeable alkaline electrochemical cell comprising a positive electrode, a negative electrode, a main separator disposed between said positive and negative electrodes, and an alkaline electrolyte in contact with said electrodes and said main separator, the improvement which comprises:

a negative interseparator disposed in said electrolyte between said main separator and said negative electrode and comprising (a) an inorganic fibrous titanate material, and (b) an inorganic fibrous matrix-forming material having a length and flexibility sufficient to form a matrix for said titanate material, said titanate material being present in an amount between about 50% and about 95% by weight of the weight of said (a) and (b), and said matrix-forming material being present in an amount sufficient to make up 100% by weight of said (a) and (b).
2. The improvement of claim 1 which further includes:
(c) a thickening agent which is relatively inert to the alkaline media in said electrochemical cells, said thickening agent being capable of increasing, and being present in amount sufficient to increase, the viscosity of a slurry of said (a) and (b) from which said negative interseparator may be formed, said titanate material being present in an amount between about 50% and about 95% by weight of the weight of said (a), (b) and (c), and said thickening agent and said matrix-forming material being present in a combined amount to make up 100% by weight of the weight of said (a), (b) and (c).
3. The improvement of claim 2 wherein said matrix-forming material and said thickening agent are present in amounts between continued Claim 3.

about 4.5% and about 45% by weight and about 0.5% and about 5% by weight, respectively, of the weight of said (a), (b) and (c).
4. The improvement of claim 2 wherein said thickening agent is carboxymethyl cellulose, hydroxyethyl cellulose, ethyl cellulose, or methyl cellulose.
5. The improvement of claim 1 wherein said titanate material is potassium titanate, sodium titanate, magnesium titanate, calcium titanate, cerium titanate, barium titanate, magnesium-calcium titanate, or mixtures thereof.
6. The improvement of claim 1 wherein said matrix-forming material is chrysotile asbestos, zirconia fibers, alumino-silicate fibers or alumina fibers.
7. The improvement of claim 1 wherein a portion of said matrix-forming material is of colloidal size, the remainder of said matrix-forming material being present in amount sufficient to form a matrix for said titanate material.
8. The improvement of claim 1 wherein said titanate material is present in an amount between about 75% and about 92%
by weight of the weight of said (a) and (b).
9. The improvement of claim 2 wherein said (a), (b) and (c) are present in amounts between about 75% and about 92%, between about 8% and about 25%, and between about 0.5% and about 2.5% by weight of the weight of said (a), (b) and (c), respectively.
10. The improvement of claim 1 wherein the length of said matrix-forming material is between about 200 and about 500 microns.
11. A composite structure for use as a negative inter-separator in a rechargeable alkaline electrochemical cell, comprising:
(a) an inorganic titanate material, and (b) an continued Claim 11.

inorganic fibrous matrix-forming material having a length and flexibility sufficient to form a matrix for said titanate material, said titanate material being present in an amount between about 50% and about 95% by weight of the weight of said (a) and (b), and said matrix-forming material being present in an amount sufficient to make up 100% by weight of said (a) and (b).
12. The composite structure of claim 11 which further includes:
(c) a thickening agent which is relatively inert to alkaline media in rechargeable alkaline electrochemical cells, said thickening agent being capable of increasing, and being present in amount sufficient to increase, the viscosity of a slurry of said (a) and (b) from which said composite structure may be formed, said titanate material being present in an amount between about 50% and about 95% by weight of said (a), (b) and (c), and said thickening agent and said matrix-forming material being present in a combined amount to make up 100% by weight of the weight of said (a), (b) and (c).
13. The composite structure of claim 12 wherein said matrix-forming material and said thickening agent are present in amounts between about 4.5%-and about 45% by weight and about 0.5%
and about 5% by weight, respectively, of the weight of said (a), (b) and (c).
14. The composite structure of claim 12 wherein said thickening agent is carboxymethyl cellulose, hydroxyethyl cellulose, ethyl cellulose, or methyl cellulose.
15. The composite structure of claim 11 wherein said titanate material is potassium titanate, sodium titanate, magnesium titanate, calcium titanate, cerium titanate, barium titanate, magnesium-calcium titanate, or mixtures thereof.
16. The composite structure of claim 11 wherein said matrix-forming material is chrysotile asbestos, zirconia fibers, alumino-silicate fibers or alumina fibers.
17. The composite structure of claim 11 wherein a portion of said matrix-forming material is of colloidal size to serve as a thickening agent when forming said structure from a fluid medium, the remainder of said matrix-forming material being present in amount sufficient to form a matrix for said titanate material.
CA283,581A 1976-07-27 1977-07-27 Separator for secondary alkaline batteries Expired CA1073044A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US05/709,136 US4034144A (en) 1976-07-27 1976-07-27 Separator for secondary alkaline batteries

Publications (1)

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CA1073044A true CA1073044A (en) 1980-03-04

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Country Status (8)

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US (1) US4034144A (en)
JP (1) JPS5836823B2 (en)
CA (1) CA1073044A (en)
DE (1) DE2733690A1 (en)
FR (1) FR2360179A1 (en)
GB (2) GB1555586A (en)
IL (1) IL52567A (en)
IT (1) IT1079376B (en)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2938123A1 (en) * 1979-09-20 1981-04-09 Siemens AG, 1000 Berlin und 8000 München DIAPHRAGMS FOR ELECTROCHEMICAL CELLS AND THEIR PRODUCTION
US4277547A (en) * 1980-03-10 1981-07-07 Hughes Aircraft Company Alkaline battery spearator
US4363834A (en) * 1980-03-10 1982-12-14 Hughes Aircraft Company Process for preparing wettable composites from inert organic polymer fibers with inorganic particles
DE3337570C2 (en) * 1983-10-15 1986-03-13 Varta Batterie Ag, 3000 Hannover Galvanic primary element that can be discharged at high temperatures
JPS61214357A (en) * 1985-03-19 1986-09-24 Japan Vilene Co Ltd Alkaline cell separator
US4818735A (en) * 1986-02-14 1989-04-04 National Institute For Research In Inorganic Materials Tetragonal system tunnel-structured compound AX(GA8MYGA(8+X)-YTI16-X0 56), and cation conductor and heat insulating material composed thereof
US5208121A (en) * 1991-06-18 1993-05-04 Wisconsin Alumni Research Foundation Battery utilizing ceramic membranes
US20020012848A1 (en) * 1999-02-26 2002-01-31 Callahan Robert W. Electrochemical cell incorporating polymer matrix material
US6849702B2 (en) 1999-02-26 2005-02-01 Robert W. Callahan Polymer matrix material

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3364077A (en) * 1964-06-29 1968-01-16 Mc Donnell Douglas Corp Battery separator and battery
US3861963A (en) * 1968-02-23 1975-01-21 Mc Donnell Douglas Corp Battery separator construction
US3539396A (en) * 1968-11-05 1970-11-10 Us Army Rechargeable alkaline zinc system
US3625771A (en) * 1969-03-27 1971-12-07 Mc Donnell Douglas Corp Battery separator
US3647554A (en) * 1969-04-17 1972-03-07 Mc Donnell Douglas Corp Battery separator and method of producing same
US3711336A (en) * 1970-08-05 1973-01-16 Mc Donnell Douglas Corp Ceramic separator and filter and method of production

Also Published As

Publication number Publication date
FR2360179A1 (en) 1978-02-24
US4034144A (en) 1977-07-05
DE2733690C2 (en) 1981-09-24
JPS5836823B2 (en) 1983-08-11
IL52567A0 (en) 1977-10-31
GB1557775A (en) 1979-12-12
IL52567A (en) 1979-09-30
JPS5319538A (en) 1978-02-22
DE2733690A1 (en) 1978-02-02
GB1555586A (en) 1979-11-14
FR2360179B1 (en) 1980-04-18
IT1079376B (en) 1985-05-08

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