CA1121667A - Polypropylene separator for use in alkaline storage batteries and process for making same - Google Patents

Polypropylene separator for use in alkaline storage batteries and process for making same

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Publication number
CA1121667A
CA1121667A CA000336854A CA336854A CA1121667A CA 1121667 A CA1121667 A CA 1121667A CA 000336854 A CA000336854 A CA 000336854A CA 336854 A CA336854 A CA 336854A CA 1121667 A CA1121667 A CA 1121667A
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CA
Canada
Prior art keywords
solvent
solution
polymer
fabric
polybenzimidazole
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
CA000336854A
Other languages
French (fr)
Inventor
Scott A. Verzwyvelt
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.)
AT&T MVPD Group LLC
Original Assignee
Hughes Aircraft Co
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 Hughes Aircraft Co filed Critical Hughes Aircraft Co
Application granted granted Critical
Publication of CA1121667A publication Critical patent/CA1121667A/en
Expired legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/59—Polyamides; Polyimides
    • 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
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • 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
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
    • 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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Textile Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Cell Separators (AREA)

Abstract

IMPROVED POLYPROPYLENE SEPARATOR Scott A. Verzwyvelt FOR USE IN ALKALINE STORAGE
BATTERIES AND PROCESS FOR MAKING SAME

ABSTRACT OF THE DISCLOSURE

Intrinsically nonwettable polypropylene battery separators are rendered wettable by treating them with polybenzimidazole.
Polybenzimidazole (PBI) treated polypropylene (PP) separators exhibited excellent thermal and chemical stabilities, show excellent electrolyte retention, and are gas permeable.

Description

11216~i7 FIELD OF THE INVENTION
This invention relates generally to the fabrication of separators for use in alkaline storage batteries and particularly to the improvement of polypropylene separators designed to be employed in nickel cadmium storage batteries.
In an even more specific aspect, the present invention resides in the provision of a wettable coating for intrinsically non-wettable polypropylene and other non-wettable chemically inert polymers.

BACKGROUND OF THE INVENTION
A life limiting factor in the design of nickel cadmium batteries has been the life of the separators utilized in the fabrication of the batteries. The nickel-cadmium spacecraft batteries utilize aqueous potassium hydroxide (KOH) solutions as the elctrolyte, and operate under electrolyte starved conditions. State-of-the-art nickel-cadmium batteries contain separators fabricated from either a nylon or poly-propylene felt that has been treated with a wetting agent.
These separators are life limited because of the chemical instability of nylon and the chemical instability of the poly-propylene wetting agent in the battery electrolyte.
In particular polypropylene battery separators, because of the intrinsic non-wettability of the material, tend to cause battery failures because of separator dry outs and low electrolyte retention. Attempts to solve this problem by adding wetting agents to the polypropylene separators have been unsuccessful because of the instability of the .
~ ` ` '':

.:

wetting agents when exposed to aqueous potassium hydroxide solutions.
It is therefore an objective of the invention disclosed herein to provide an improved separator for use in alkaline storage batteries; an additional objective of the invention disclosed herein is to provide a novel means for increasing the wettability of polypropylene and other intrinsically non-wettable chemically inert materials designed to be used as separators for storage batteries; and a still further objective of this invention is to provide an inexpensive stable porous organic separator for use in alkaline storage batteries.

SUMMARY OF THE INVENTION
To accomplish the above-stated objectives and provide an improved porous organic separator for use in alkaline storage batteries, it has been discovered that intrinsically non-wettable polymers, such as polyethylene, polypropylene, etc., can be coated with a wettable, in aqueous KOH solutions, polymer and thereby rendered suitable for use in the fabrication of battery separators having improved electrolyte retention characteristics and excellent chemical stability without altering other properties of the polymers.
Polymer fabrics manufactured from a group of chemically inert intrinsically non-wettable polymers such as polyethylene, and polypropylene are immersed in and saturated with a coating solution comprised of a chemically stable wettable polymer dissolved in a polar solvent. The solvent is removed by evaporation or precipitation techniques and a thin film of the stable wettable polymer is retained by the fibers of B

.

- : . : .

llZ16~7 the fabric.
When dried at temperatures not to exceed 100~C, the coated fabric is wettable in aqueous KOH solutions, retains electrolytes and is chemically stable.
The coatings and coating process of this invention are suitable for providing a wettable surface on intrinsically non-wettable polymer films, sheets or rods as well as fibers.
Thus in one embodiment the present invention provides a method of rendering extrinsically non-wettable polymeric fibers, films, sheet and rod surfaces wettable, comprising the steps of providing a thin coating of a wettable polymer selected from the group consisting of polybenzimidazole, polybenzoxazole, and polybenzothiazole deposited onto the surface of said fibers, films, sheets and rods from a polymer-solvent solution, removing said solvent and drying said coating at a selected temperature.
In a closely related embodiment, the invention provides such a process which is adapted to providing an improved organic separator that is chemically resistant to and wettable by an aqueous KOH solution for use in alkaline storage batteries comprising the steps of:
a. providing an uncontaminated fabric comprised of fibers selected from the group consisting of poly-ethylene, polypropylene and polybutylene, suitable for use as a separator;
b. forming a coating solution by dissolving a polymer selected from the group consisting of polybenzimidazole, polybenzoxazole, and polybenzothiazole in a selected polar solvent;

c. immersing said fabric in said solution and allowing said fabric to soak in said solution until saturated while maintaining a constant polymer-solvent concentra-tion;
d. sequentially removing said saturated fabric from said soaking solution and removing any excess soaking solution from said fabric thereby leaving said fabric impregnated and coated with the solvent and polymer of said soaking solution;
e. causing said solvent to be removed from said coating solution by subjecting said fabric to a solvent removal technicque selected from the group consisting of solvent evaporation and solvent precipitation; and f. drying said coated fabric at an elevated temperature prior to use as a battery separator.
In a further aspect, the invention provides an improvement in porous polypropylene separators intended for use in alkaline storage batteries wherein said improvement consists of a thin coating of a stable polymer selected from the group consist-ing of polybenzimidazole, polybenzoxazole, and polybenzothiazoleapplied to the surface of said separator, which provides a wettable surface capable of resisting the chemical action of aqueous KOH electrolytes while retaining said electrolytes within the pores of said separator.
In still a further aspect, the invention provides in an alkaline storage battery having electro members, spaced apart by organic separators which retain a liquid electrolyte and provide a current path between said electrodes, an improved organic separator comprising a porous substrate of non-wettable fibers ~0 selected from the group consisting of polyethylene, polypropyl-~ , :

: ; :

ene and polybutylene first polymers having a multiplicity of interstices and a thin layer of thermally stable wettable polybenzimidazole polymer formed around and about said fibers which permanently adheres to said fibers,without altering the structural characteristics of said fibers, to render them wettable in aqueous potassium hydroxide solution and permits the passage of ions and gases through said separator.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
This invention describes the treatment of nonwettable polymer substrates such as polypropylene with wettable polybenzimidazole. The resultant wettable material is suitable for application as a separator material in alkaline storage batteries such as nickel cadmium batteries. Poly-propylene is chemicallyinert and intrinsically nonwettable.
Polybenzimidazole is also chemically inert, but is very wettable in aqueous solutions. In the technique described below it is possible to coat polypropylene permanently with polybenzimidazole. The coating of polybenzimidazole affords the polypropylene substrate with good electrolyte wettability, vastly improved electrolyte retention, and better ionic conduc-tivity in the electrolyte wet state. At the same time, the structural form of the polypropylene substrate is unchanged and therefore the original gas permeability is largely retained.
The treatment of polypropylene with PBI is accomplished in the following general manner: the polypropylene substrate is washed with acetone or 100 water to remove any contaminants and dried. Subsequently, it is immersed in an impregnation solution of PBI dissolved in dimethylacetamide (DMA), ,~ .
' 112i667 dimethylsulfoxide (DMSO), or dimethylformamide (DMF). The PBI solution wetted sample is removed, drained, and blotted under controlled compression for a specified time period.
Physical parameters such as blotting time, temperature and compression are monitored and controlled to insure reproducible results. Then, the solvent is either evaporated off leaving the PBI coating on the surface of the polypropylene fibers or the PBI
is precipitated on the surface of the fibers by treating with an extractant liquid in which PBI is insoluble and the PBI solvent is miscible. Finally, the sample was dried in an oven.
The polybenzimidazole coating achieved by precipitation demonstrates superior wettability and electrolyte retention.
In the evaporation and drying steps B
-5a-: . ~
-.

ilZ1667 ~~ 6 1 of the techniclue, it is importdnt not to excee~ the meltin~
2 point of the polypropylene or inert polymer substrate.
3 The initial structure of the polypropylene is important in determining electrode spacing, gas permeability and dendrite penetration. It is pos~lble to increase ~lectroly~e retention, 6 ~lect~olyte wettability and to some extent ~as perr,~eability 7 by tlC~t only the method oE coating (evaporative or precipitative), 8 but in the case of precipitation, by the quantity of poly-g benzimidazole loadin~. By increasing the impregnation solution concentration, by reducing the extent of draining 11 and blotting, and by successive layers of coatings it is 12 possible to apply thicker layers of polybenzimidazole. This 13 can potentially increase electrolyte wettability, electrolyte 14 retention, but may, if brought to an extreme, reduce gas permeability. This should allow some latitude in the separator 16 characteristics when specific requirements are present.

19 Prepare a mixture of PBI and DMA by adding 15 grams of PBI and 0.03 grams of lithium chloride to 100 ml of DMA.
21 Reflux and stir for 16 hours or until essentially all of 22 the PBI is dissolved into the DMA. Filter to remove any 23 undissolved PBI from the resulting solution and allow to 24 cool.
Remove all traces of surfactants and/or other 26 contaminants from the surfaces of a polypropylene ~abric by 27 washing the fabric in boiling water and acetone.

, ~121~

1 Dry ~he w~shed fabric and immersc in the PBI/~IA
2 solution or at least 15 minutes. The irnmersion step should 3 be performed in a container provided with a means for precluding
4 the loss of solvent from the solution by evaporation.
The soa~ed fabric o,r sample is then removed from 6 the PBI/VIi~ solu.ion, allowed to drain and blotted to remove 7 excess PBI/DMA solution from the surface ~lhich leavcs a 8 coating of PBI and DMA on the surface of the fibers of g the fabric.
The PBI solution wetted polypropylene is then immersed 11 in an extractant liquid (H20 at 100C). This immersion is ----12 accomplished while holding the sample in a plane vertical to 13 the liquid surface. The~sample is left in the extractant 14 liquid for at least 5 minutes before removal where it is 15 dried at 100C in an air oven. The 100 water extracts 16 the solvent (D~A) from the'impregnation solution, thereby 17 precipitating a PBI film on the polypropylene fibers.
18 The resultant PBI adhesion to polypropylene is good.

EXAMPLE II
21 Prepare a solution of 5% w/v PBI in dimethyl~ormamide 0~07S~ fo O.tS~
22-and add from l.5 to ~.0~ lithium chloride to stabilize the 23 SOlUtion, 24 Remove all contaminants from a polypropylene felt by 25 washing the felt in acetone and drying it in air.
26 Immerse the felt in the PBI solution and blot to 27 remove excess solution as described in Example I.
28 Place the blotted sample on a screen in a vacuum oven ~ - \
- l~Z16~;7 1 and remove the solvent ~rom the coatiny ~y ~lling a 2 vacuum on thc coated sample for four hours at 100C. The 3 sample should be isolated ~rom any heat sinks as it is 4 placed in the oven.
Samples prepared in this Inanner ar~ coated with a 6 thin film of PBI and tend to be less wettable in KOIl than 7 samples prepared via precipitation of the polymer from tne 8 po~ymer solvent solution as in Example I.

EXAMPLE III
11 Remove all contaminants from a tetrafluorethylene 12 30-50~ microporous membrane by washing it in acetone and 13 drying it in air.
14 Place the decontaminated sample in a vacuum chamber 15 adapted to provide a liquid to said chamber under vacuum.
16 Allow a 7~ w/v PBI/DMA impregnation solution to be 17 vacuum backfilled into the pores of said membrane. Vacuum 18 backfilled is intended to describe the process of allowing 19 a liquid to flow onto a porous membrane under vacuum. This 20 affords better penetration of the polymer into the pores of 21 the membrane 22 Remove the impregnated sample from the chamber and 23 blot to remove excess solution from the surface as described 24 in Example I.
Extract the solvent from the solution impregnated 26 sample by the precipitation process described in Example I.

., `` 11~1t~67 _ 9 _ Polypropylene and nylon ro~s are wasl-~ed in acetone to remove surface contaminants prior to their immcrsion in a PBI!DI~IA solution prepared in accordance with the metnod of ~xample I~
Excess solu~ion is allo~ed to drain from ~he surface o~
the rods and the solvent is extracted from the soluti.on ~y either o~ the processes tauyht above.
The net results are solid rods coated with a wettable layer of PBI which adheres to the rods.

28 Blr~: aq [52-4~

Claims (7)

1. A method of rendering extrinsically non-wettable polymeric fibers, films, sheet and rod surfaces wettable, comprising the steps of providing a thin coating of a wettable polymer selected from the group consisting of polybenzimidazole, polybenzoxazole, and polybenzothiazole deposited onto the surface of said fibers, films, sheets and rods from a polymer-solvent solution, removing said solvent and drying said coating at a selected temperature.
2. The method of claim 1, wherein said wettable polymer is removed from said polymer-solvent solution by a precipitation process which leaves particles of said polymer adhering to the surface of said fibers, films, sheets and rods.
3. The method of claim 1 or 2, wherein said coating is comprised of polybenzimidazole deposited from a solution of polybenzimidazole and dimethylacetamide.
4. The process of claim 1 which is adapted to providing an improved organic separator that is chemically resistant to and wettable by an aqueous KOH solution for use in alkaline storage batteries comprising the steps of:
a. providing an uncontaminated fabric comprised of fibers selected from the group consisting of polyethylene, polypropylene, and polybutylene, suitable for use as a separator;
b. forming a coating solution by dissolving a polymer selected from the group consisting of polybenzimidazole, polybenzoxazole, and polybenzothiazole in a selected polar solvent;

c. immersing said fabric in said solution and allowing said fabric to soak in said solution until saturated while maintaining a constant polymer-solvent concentration;
d. sequentially removing said saturated fabric from said soaking solution and removing any excess soaking solution from said fabric thereby leaving said fabric impregnated and coated with the solvent and polymer of said soaking solution;
e. causing said solvent to be removed from said coating solution by subjecting said fabric to a solvent removal technique selected from the group consisting of solvent evaporation and solvent precipitation; and f. drying said coated fabric at an elevated temperature prior to use as a battery separator.
5. The process of claim 4 wherein said separator fabric is polypropylene, said polymer is polybenzimidazole, and said selected solvent is dimethylacetamide.
6. An improvement in porous polypropylene separators intended for use in alkaline storage batteries wherein said improvement consists of a thin coating of a stable polymer selected from the group consisting of polybenzimidazole, polybenzoxazole, and polybenzothiazole applied to the surface of said separator, which provides a wettable surface capable of resisting the chemical action of aqueous KOH electrolytes while retaining said electrolytes within the pores of said separator.
7. The improvement of claim 6 wherein said coating is a thin coating of polybenzimidazole.
CA000336854A 1978-10-23 1979-10-02 Polypropylene separator for use in alkaline storage batteries and process for making same Expired CA1121667A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US05/953,511 US4217404A (en) 1978-10-23 1978-10-23 Polypropylene separator for use in alkaline storage batteries and process for making same
US953,511 1978-10-23

Publications (1)

Publication Number Publication Date
CA1121667A true CA1121667A (en) 1982-04-13

Family

ID=25494115

Family Applications (1)

Application Number Title Priority Date Filing Date
CA000336854A Expired CA1121667A (en) 1978-10-23 1979-10-02 Polypropylene separator for use in alkaline storage batteries and process for making same

Country Status (4)

Country Link
US (1) US4217404A (en)
CA (1) CA1121667A (en)
FR (1) FR2440084A1 (en)
GB (1) GB2038206B (en)

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4298666A (en) * 1980-02-27 1981-11-03 Celanese Corporation Coated open-celled microporous membranes
US4359510A (en) * 1980-07-31 1982-11-16 Celanese Corporation Hydrophilic polymer coated microporous membranes capable of use as a battery separator
US5114804A (en) * 1981-08-13 1992-05-19 Moli Energy Limited Battery and method of making the battery
US4471038A (en) * 1983-12-02 1984-09-11 At&T Bell Laboratories Nickel-cadmium battery
US4550064A (en) * 1983-12-08 1985-10-29 California Institute Of Technology High cycle life secondary lithium battery
DE3574936D1 (en) * 1984-09-17 1990-02-01 Mitsubishi Rayon Co HYDROPHILIZED MEMBRANE FROM A POROUS, HYDROPHOBIC MATERIAL AND METHOD FOR THE PRODUCTION THEREOF.
FR2579025B1 (en) * 1985-03-15 1987-04-10 Occidental Chem Co IMPROVED SEPARATION FUEL CELL
CA2085380C (en) * 1991-12-27 2005-11-29 Celgard Inc. Porous membrane having single layer structure, battery separator made thereof, preparations thereof and battery equipped with same battery separator
JP3217452B2 (en) 1992-06-09 2001-10-09 クラリアント インターナショナル リミテッド Method for forming polybenzimidazole coating
JP3482606B2 (en) * 1994-08-11 2003-12-22 日本電池株式会社 Sealed alkaline storage battery
US6159634A (en) * 1998-04-15 2000-12-12 Duracell Inc. Battery separator
US6670077B1 (en) * 2000-09-29 2003-12-30 Eveready Battery Company, Inc. Impregnated separator for electrochemical cell and method of making same
WO2011039737A1 (en) * 2009-09-30 2011-04-07 Paltechnica Improved ballistic resistant composite articles with polydicyclopentadiene (pdcpd)
KR101670200B1 (en) * 2010-08-02 2016-10-27 셀가드 엘엘씨 High melt temperature microporous lithium-ion rechargeable battery separators and methods of preparation and use
CN108320916A (en) * 2010-08-02 2018-07-24 赛尔格有限责任公司 The partition board and its correlation technique of superelevation melt temperature microporous high-temperature battery
US9199199B2 (en) * 2012-10-05 2015-12-01 Uop Llc Separation membrane
US20240194902A1 (en) * 2022-12-07 2024-06-13 Standard Energy Co., Ltd. Polybenzimidazole-based separator for secondary battery, and method of preparing fabricating same and secondary battery comprising the same

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3929509A (en) * 1972-04-18 1975-12-30 Celanese Corp Hydrophilic microporous film
US3933525A (en) * 1972-12-21 1976-01-20 W. R. Grace & Co. Battery separator manufacturing process
US3856549A (en) * 1973-06-04 1974-12-24 R Dauksys Method for stabilizing polybenzimidazoles
US4110143A (en) * 1974-10-21 1978-08-29 W. R. Grace & Co. Process for making a wettable polyolefin battery separator
US4122133A (en) * 1977-03-23 1978-10-24 Esb Incorporated Material for an alkaline cell separator and a process of making

Also Published As

Publication number Publication date
GB2038206B (en) 1982-08-18
FR2440084B1 (en) 1983-05-27
FR2440084A1 (en) 1980-05-23
US4217404A (en) 1980-08-12
GB2038206A (en) 1980-07-23

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