WO1999001733A1 - Organic solvent vapor detector - Google Patents
Organic solvent vapor detector Download PDFInfo
- Publication number
- WO1999001733A1 WO1999001733A1 PCT/US1998/013121 US9813121W WO9901733A1 WO 1999001733 A1 WO1999001733 A1 WO 1999001733A1 US 9813121 W US9813121 W US 9813121W WO 9901733 A1 WO9901733 A1 WO 9901733A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- detector
- polymeric material
- swellable polymeric
- electrically conductive
- conductive particles
- Prior art date
Links
- 239000003960 organic solvent Substances 0.000 title description 2
- 239000000463 material Substances 0.000 claims abstract description 91
- 239000007788 liquid Substances 0.000 claims abstract description 61
- 239000002245 particle Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 22
- 229920000642 polymer Polymers 0.000 claims abstract description 18
- 230000008569 process Effects 0.000 claims abstract description 16
- 229920001577 copolymer Polymers 0.000 claims abstract description 14
- 239000006069 physical mixture Substances 0.000 claims abstract description 10
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000010408 film Substances 0.000 claims description 45
- 239000011248 coating agent Substances 0.000 claims description 23
- 238000000576 coating method Methods 0.000 claims description 23
- 229910052709 silver Inorganic materials 0.000 claims description 11
- 239000010409 thin film Substances 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 8
- 230000008859 change Effects 0.000 claims description 8
- 239000004332 silver Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229920001973 fluoroelastomer Polymers 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229920000058 polyacrylate Polymers 0.000 claims description 4
- 238000007639 printing Methods 0.000 claims description 4
- 229920006332 epoxy adhesive Polymers 0.000 claims description 3
- 230000001747 exhibiting effect Effects 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 239000011135 tin Substances 0.000 claims description 3
- 239000002174 Styrene-butadiene Substances 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical group C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims description 2
- 230000001680 brushing effect Effects 0.000 claims description 2
- RTACIUYXLGWTAE-UHFFFAOYSA-N buta-1,3-diene;2-methylbuta-1,3-diene;styrene Chemical compound C=CC=C.CC(=C)C=C.C=CC1=CC=CC=C1 RTACIUYXLGWTAE-UHFFFAOYSA-N 0.000 claims description 2
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 claims description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 230000001413 cellular effect Effects 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229920001084 poly(chloroprene) Polymers 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 229920001021 polysulfide Polymers 0.000 claims description 2
- 239000005077 polysulfide Substances 0.000 claims description 2
- 150000008117 polysulfides Polymers 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 239000011115 styrene butadiene Substances 0.000 claims description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
- 238000010345 tape casting Methods 0.000 claims description 2
- 150000003673 urethanes Chemical class 0.000 claims description 2
- 229920006112 polar polymer Polymers 0.000 claims 2
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 claims 1
- 229920005549 butyl rubber Polymers 0.000 claims 1
- 229920006037 cross link polymer Polymers 0.000 claims 1
- 239000011521 glass Substances 0.000 claims 1
- 229920003049 isoprene rubber Polymers 0.000 claims 1
- 229920006113 non-polar polymer Polymers 0.000 claims 1
- -1 poly(ethylene terephthalate) Polymers 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- 239000004593 Epoxy Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 6
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 6
- 230000004044 response Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 230000008961 swelling Effects 0.000 description 5
- 229910001290 LiPF6 Inorganic materials 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229920006267 polyester film Polymers 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- XCEDYBCDZCQLER-UHFFFAOYSA-N 2-methylbuta-1,3-diene;prop-2-enenitrile;styrene Chemical compound C=CC#N.CC(=C)C=C.C=CC1=CC=CC=C1 XCEDYBCDZCQLER-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229920002449 FKM Polymers 0.000 description 1
- 239000005041 Mylar™ Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 239000005035 Surlyn® Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000002828 fuel tank Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 230000011664 signaling Effects 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
- G01N27/126—Composition of the body, e.g. the composition of its sensitive layer comprising organic polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/48—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte
- H01M10/488—Cells or batteries combined with indicating means for external visualization of the condition, e.g. by change of colour or of light density
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/0004—Gaseous mixtures, e.g. polluted air
- G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
- G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
- G01N33/0036—General constructional details of gas analysers, e.g. portable test equipment concerning the detector specially adapted to detect a particular component
- G01N33/0047—Organic compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4285—Testing apparatus
-
- 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
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/569—Constructional details of current conducting connections for detecting conditions inside cells or batteries, e.g. details of voltage sensing terminals
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2291/00—Indexing codes associated with group G01N29/00
- G01N2291/02—Indexing codes associated with the analysed material
- G01N2291/028—Material parameters
- G01N2291/02863—Electric or magnetic parameters
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4228—Leak testing of cells or batteries
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/0266—Marks, test patterns or identification means
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates generally to the art of an organic liquid and/or vapor detector and more specifically to a battery pack detector which can be used in conjunction with a battery operated device or an intelligent on-board battery controller.
- the detector of the present invention comprises an organic liquid swellable polymeric material which, optionally, may contain electrically conductive particles dispersed therein.
- the detector of the present invention which may be supported or unsupported, is highly sensitive in detecting organic liquids and/or vapors typically found in rechargeable or primary batteries as well as the level of such organic liquids in a container.
- intelligent portable electronic devices such as notebook computers, video cameras, cellular phones and the like has enabled the development of rechargeable and primary batteries that maintain safety and in some instances, can communicate with the intelligent device to provide accurate information on the battery's present state of charge, and how best to recharge the battery to maintain maximum battery life, thus enabling the highest number of charge-discharge states.
- a user of such intelligent portable electronic devices, using such batteries, will not only know how much charge is left in the battery, but battery run time at various rates of power consumption. This enables the user to select a mode of operation that will enable maximum service life on the remaining state of charge and, how long the device will operate.
- one object of the present invention is to provide a detector that can be used in a battery pack or in conjunction with an intelligent portable electronic device.
- Another object of the present invention is to provide a detector which is highly sensitive to polar and/or non-polar organic liquids and/or vapors and thus provides a rapid response if such organic liquids and/or vapors are emitted by a nearby battery cell or other source containing such organic liquids and/or vapors.
- a further object of the present invention is to provide a detector which can be used to detect leaks in various devices and/or the fluid level of an organic liquid in a container.
- Another object of the invention is to provide a reversible response. That is, the detector is capable of signaling the removal of organic liquid and/or vapor from a container.
- a detector which comprises a supported or unsupported organic liquid swellable polymeric material which, optionally, may contain electrically conductive particles dispersed therein. That is, the detector of the present invention comprises a swellable polymeric material which is capable of exhibiting volume changes when exposed to an organic liquid and/or vapor.
- any change in the volume of the polymeric material as a result of liquid swelling can subsequently produce an electrical signal response such as a change in resistivity, capacitance or transducer acoustical inductance.
- the nature of the polymeric material is dependent upon the solubility parameters such as polarity and hydrogen bonding index of the target liquid. Generally, the solubility parameters of the polymeric material is similar to the target liquid.
- the polymeric material is composed of a polar swellable polymeric material.
- a non-polar swellable polymeric material is used for detecting non-polar organic liquids and/or vapors.
- the polymeric material When operating in the preferred resistance mode, the polymeric material is filled with electrically conductive particles and electrically bonded between electrically conductive terminals.
- the polymeric material can be coated onto at least one side of a mechanically supporting carrier, or it can be unsupported. Organic liquid swelling of the polymeric material increases the distance between the dispersed electrically conductive particles resulting in a corresponding electrical resistance increase.
- the preferred geometry of the polymeric material operating in the resistive mode is a supported or unsupported thin film.
- the rate of change of the electrical signal response is proportional to the rate of swelling of the polymeric material. In order to maximize the response time, the mass ratio of the polymeric material to target organic liquid or vapor must be minimized and this can be achieved with thin film geometry.
- the polymeric material can be operated in the capacitive mode and is achieved by sandwiching the polymeric material, preferably as a thin film, between two electrically conductive porous or nonporous plates. Exposure to an organic liquid and/or vapor induces swelling of the polymeric material and produces a corresponding change in the distance between the conductive plates resulting in a capacitive signal.
- the polymeric material can be operated in an acoustical conductive mode by mechanically attaching the polymeric material between two mechanical transducers (a transmitter and receiver), such as is present in a surface acoustical wave (SAW) device. Exposure to an organic liquid and/or vapor produces a change in the acoustical conduction properties of the swollen polymeric material resulting in a corresponding modulation of the transducer signal.
- SAW surface acoustical wave
- the detector is fabricated by either printing the swellable polymeric material using printing techniques well known to those skilled in the art directly across two electrically conductive circuit traces on a printed circuit board, or as a separate supported film component which is subsequently electrically connected to a circuit.
- An example of the latter method is as follows: providing the above mentioned polymeric material coated support film; diecutting said polymeric coated support film to provide a material having a resistance of from about 100 to about 1 Megohms/sq.; and attaching electrically conductive wires to said diecut film or directly bonding the diecut film to a circuit board.
- a further aspect of the present invention relates to various devices such as smoke detectors, fire alarms and battery packs for camcorders and the like which contain the detector of the present invention.
- a terminal means for connecting the battery pack to a battery powered device a battery including at least one rechargeable or primary battery cell connected to said terminal means, and the detector of the present invention connected to the battery. This set-up allows for the detection of leaks by the nearby battery cell.
- the detector is utilized as a continuous level indicator to monitor the amount of fluid in a container.
- This aspect of the present invention is predicated on the ability of the polymeric material to return to substantially the same form as prior to liquid contact.
- Figure 1 is a cross-sectional view of a detector of the present invention comprising an unfilled organic liquid and/or vapor swellable polymeric material which is sandwiched between two electrically conductive plates.
- Figure 2 is a cross-sectional view of a detector of the present invention comprising an electrically conductive filled organic liquid and/or vapor swellable polymeric material supported on a polymer base.
- Figure 3 is an electronic diagram showing the detector of the present invention in use in a Duracell Battery Operating System (hereinafter 'DBOS').
- 'DBOS' Duracell Battery Operating System
- the detector of the present invention comprises an organic liquid and/or vapor swellable polymeric material that, optionally, may be filled with electrically conductive particles.
- swellable polymeric material it is meant any polymer, copolymer or physical mixture thereof which upon contact with an organic liquid and/or vapor exhibits volume expansion. It is noted that after the organic liquid and/or vapor is removed, the polymeric material returns to its original volume.
- the detector of the present invention may be in any geometric form or shape such as cubic, spherical or thin film.
- a preferred geometric form of the detector of the present invention is a thin film.
- the detector of the present invention may be supported on a carrier material or it may be unsupported depending upon its mode of operation.
- a capacitive detector 10 which comprises an organic liquid and/or vapor swellable polymeric material 14 that is sandwiched between conductive plates 16 and 16'.
- Conductive plates 16 and 16' employed in the present invention are composed of conventional conductive materials such as Cu, Ag, brass, Sn, Ni, Au and the like.
- polymeric material 14 is not filled with an electrically conductive material. If plates 16 and 16' are replaced with a transmitting and receiving mechanical transducer, the device operates as an acoustical transducer type organic liquid detector.
- detector 10 is a solid material comprising a support film 12 which is coated with an organic liquid and/or vapor swellable polymeric material 14 that is filled with electrically conductive particles.
- support film 12 may be a printed circuit board or card wherein the filled organic liquid and/or vapor swellable polymeric material is coated or printed oh the surface thereof.
- Support film 12 that is employed in the present invention as a carrier material may be any non-electrically conductive material that is not dissolved or the integrity of which is not adversely affected by the matrix coating solvent.
- Preferred materials are polymer films, sheets or laminates such as polyesters (including poly(ethylene terephthalate), poly(butylene terephthalate), poly (naphthelene terephthalate), aromatic heterocyclic polyimides (such as Kapton ® supplied by Dupont), polypropylene, polyethylene, polyethylene ionomers (such as Surlyn ® supplied by Dupont), polybutylene, polyvinyl fluoride, polyvinylidene chloride, polyvinyl chloride, polyamides (such as Nylon ® supplied by Dupont), ethylene vinylacetate, cellulose acetate, polyurethane and the like.
- support film 12 may be a printed circuit board or card.
- the thickness of the support film is not a critical limitation to the instant invention, but typically, the support film has a thickness which ranges from about 0.5 to about 50 mils.
- Polymeric material 14 employed in the present invention is any polar or non-polar elastomeric polymer or copolymer that is preferably crosslinked and which swells upon contact with an organic liquid and/or vapor.
- Physical mixtures of said polymers and/or copolymers are also contemplated by the instant invention.
- the term "physical mixtures" is used herein to denote an admixture of polymers and/or copolymers wherein no chemical bonding between said polymers and/or copolymers is formed. Additionally it is preferred, but not necessary, that the swellable polymeric material has a glass transition temperature below about 30°C in order to have the polymer chains mobile enough to expand upon contact with an organic liquid and/or vapor.
- Suitable polymers that may be used in forming polymeric material 14 include, but are not limited to: fiuoroelastomers, urethanes, neoprenes, polyacrylates, polysulfides, silicones, butyl and the like.
- suitable copolymers that may be employed include, but ar not limited to: acrylonitrile-butadiene, acrylonitrile- styrene-butadiene, acrylonitrile-styrene-isoprene, styrene-butadiene, styrene-butadiene- isoprene and the like.
- a highly preferred polymer employed in the present invention is a flouroelastomer such as is commercially available from Pelomer Labs under the tradename PLV 2069. It is emphasized that the above mentioned polymers and copolymers are highly sensitive to detecting polar or non-polar organic liquids and/or vapors depending on matching the respective polarity of the swellable polymer to the target organic liquid and/or vapor.
- organic liquid and/or vapor swellable polymeric material 14 When organic liquid and/or vapor swellable polymeric material 14 is filled, it is typically filled with a population of electrically conductive particles.
- the electrically conductive particles employed in the present invention are conventional conductors well known to those skilled in the art. Examples of electrically conductive particles that may be employed in the present invention include, but are not limited to: carbon black, graphite, silver, tin, gold, palladium, nickel and the like. Mixtures of these electrically conductive particles such as silver and graphite are also contemplated herein. Highly preferred electrically conductive particles that are employed in the present invention are a mixture of carbon black and graphite.
- the electrically conductive particles may be any shape. It is however preferred that the electrically conductive particles are flat shaped flakes or spherical-shaped powders. Typically, the size of the electrically conductive particles range from about 10 nm to about 100 microns. More preferably, the particle size of the electrically conductive particles is from about 0.01 to about 50 microns.
- the unfilled swellable polymeric material or the electrically conductive filled swellable polymeric material employed in the present invention may be fabricated using conventional means well known to those skilled in the art or they can be commercially obtained.
- An example of a commercially available electrically conductive filled swellable polymeric material is Electrodag 501 ® supplied by Acheson Colloids Inc. which is a combination of carbon black and graphite particles in a fluoroelastomer resin system.
- the organic liquid and/or vapor swellable polymeric material contains from about 1 to about 90%, by weight, of electrically conductive particles dispersed in the matrix of the polymeric material. More preferably, the swellable polymeric material contains from about 30 to about 70%, by weight, of electrically conductive particles.
- the organic liquid and/or vapor swellable polymeric material When supported on a base material, the organic liquid and/or vapor swellable polymeric material is in the form of a thin coating which is prepared by predispersing the conductive particles in a solvent capable of dissolving the swellable polymeric material, followed by dissolving the swellable polymeric material.
- suitable coating solvents include, but are not limited to: methyl ethyl ketone, acetone, toluene, tetrahydrofuran and the like.
- the matrix coating solution can be prepared by mixing commercially available conductive coating solutions with suitable swellable polymeric materials.
- the electrically conductive filled swellable polymeric material has a resistance of from about 20 ohm/sq. to about 1 Megohm/sq. More preferably, the resistance of the electrically conductive filled swellable polymeric material, prior to application, is from about 1 Kohm/sq to about 100 Kohm/sq and can be adjusted by varying the ratio of conductive particle mass to swellable polymeric mass.
- the filled swellable polymeric solution is cast upon, i.e. applied to at least one surface of support film 12, using conventional coating techniques well known to those skilled in the art.
- coating of the support film with the filled swellable polymeric material may be conducted by brushing, dipping, knife coating, gravure, wire bar coating, spraying and the like.
- a preferred means of applying the filled swellable polymeric coating solution to the support film is by wire bar coating.
- the support material is a circuit board or card
- the swellable polymeric material containing electrically conductive particles is either printed directly on to the circuit elements of the circuit board or card using printing techniques well known to those skilled in the art or, alternatively, it is first supported on a support film and then bonded to the circuitry found on the circuit board or card using a silver epoxy adhesive.
- a uniform coating of the filled swellable polymeric solution is applied to the surface of the support film.
- uniform it is meant that the wet coating has a thickness of from about 1 to about 30 mils. It is emphasized that the above range represents the thickness of the wet coating prior to drying.
- the coated support film is dried using conditions and techniques well known to those skilled in the art.
- One way of drying the coated film is by air drying, which, depending upon the size of the coated film and the coating solvent chosen, may take from about 0.1 to about 1.0 hrs.
- Another way of drying the coated film is by heating in an oven. Typically, when oven drying is employed, the temperature of the oven is from about 60° to about 150°C and the drying time is from about 1 to about 30 minutes. No matter which of the above drying techniques is employed, the final thickness of the coating is from about 0.1 to about 1.5 mils.
- the coated support film After drying, the coated support film is diecut to a shape which provides a resistance of from about 20 ohms/sq to about 1 Megohm/sq. Moreover, since the polymeric swelling rate is proportional to the rate of increase in the organic liquid/polymeric mass ratio, the ideal shape of the device would be a thin film.
- All of the above mentioned properties can be achieved by diecutting the coated film into a shape that maximizes the electrical path length while minimizing the overall outer dimensions, such as a "u” or "w” shaped thin film.
- the next step of the present invention is to attach electrical conductive wires 20, e.g. Ag or Cu wires, to the diecut coated film.
- the wires can be attached at any edge of the thin film but it is preferred they be attached at the most distant ends of the coated surface of the thin film.
- the wires are attached using conventional electrical bonding means well known to those skilled in the art.
- a preferred means of electrically bonding wires 20 to the diecut film is by using a silver epoxy filled thermoplastic or thermoset adhesive 18 such as a silver epoxy.
- the swellable polymeric material When the organic liquid and/or vapor swellable polymeric material is not supported on a support film, the swellable polymeric material is either positioned between two conductive plates or two transducers which are electrically connected to a circuit. In these cases, the swellable polymeric material is in the form of an unsupport thin film and is diecut as mentioned above and placed between the plates or transducers.
- the above description describes the basic form of the detector of the present invention as well as the process which is employed for fabricating the same.
- the detector of the present invention is useful in detecting organic liquids, e.g., polar and/or non-polar liquids, emitted or leaked by a nearby source containing said organic liquids.
- the detector of the present invention can be used to continuously monitor the level of an organic liquid in a container.
- the following description illustrates the use of the detector of the present invention as a leak detector in a battery pack which comprises at least one rechargeable or primary battery cell which contains a polar organic liquid as the electrolyte.
- Suitable polar organic liquids which may be present in such battery cells and thus detected by the present invention are ethylene carbonate, dimethyl carbonate, and the like. Mixtures of these polar organic liquids may also be present in the battery cell.
- rechargeable battery cell is used herein to denote rechargeable Lithium Ion (Lilon), Nickel Metal Hydride (NiMH) or Nickel Cadmium (NiCad) batteries.
- a preferred rechargeable battery employed in the present invention is a Lilon battery.
- a battery pack for detecting polar organic liquids and/or vapors which comprises terminal means for connecting the pack to a battery powered device, a battery including at least one of the aforementioned rechargeable battery cells connected to said terminal means, and a detector of the present invention electrically connected to said battery.
- the rechargeable battery cell may be replaced by a primary battery cell which is described for example in Kirk-Othmer, Encyclopedia of Chemical Technology, Third Edition, Vol. 13, 1978, pp. 503-545.
- a preferred device for alarming the user of a leak is a smart battery device, such as a Duracell Battery Operating System (DBOS) which includes ASIC (Application Specific Integrated Circuit) hardware, CPU, Analog to Digital Converter, Current Measurement Means, Temperature Measurement Means, Pack- Voltage Measurement Means, Cell Voltage Measurement Means, ROM, RAM, RAM Data Back-Up Circuit, 12C/SMBUS Interface, Clock generator circuit, Wake-up comparator circuit, LED Drivers, Interface Circuits, Hardware Modes of operation, Run Mode: Entry/Exit, Sample Mode: Entry/Exit and Sleep Mode: Entry/Exit.
- ASIC Application Specific Integrated Circuit
- Fig. 3 shows the use of a detector of the present invention comprising a supported swellable polymeric material which is filled with electrically conductive particles in a typical DBOS module.
- Cl, C2 and C3 denote Lilon cells which are connected in series with each other; Ql and Q2 are transistors which are connected to the Lilon cells through resistor R5; FI is a fuse; Rl and VI are the resistance and the voltage between the positive and negative terminal ends, respectively.
- the detector of the present invention is also positioned between the positive and negative terminal ends of the DBOS module.
- the module has two major functional blocks, namely overvoltage protection and fuel gauging whose functions are described in more detail in the aforementioned copending applications. It also contains an electronic switch circuit and data communication ports, I2C and port, respectively, which are typically connected to a computer.
- the detector of the present invention when the detector of the present invention is exposed to a polar organic liquid and/or vapor, its electrical resistance rises increasing the voltage VI.
- the electronic switch circuit shown in Fig. 3 is designed to trip in response to increasing voltage such that it provides a low resistance path and blows fuse FI.
- the detector or the present invention may be employed in other areas wherein organic liquids (polar and/or non-polar) and/or vapors are emitted into the atmosphere.
- Examples of other uses for the detector of the present invention include, but are not limited to: solvent storage areas, naval bilge compartments, chemical vapor hoods, fire alarms, smoke stacks, car engine compartments, solvent coating manufacturing operations and the like.
- solvent storage areas For example, when used in a boat bilge, if gasoline (a non-polar liquid) were to leak from an adjacent fuel tank, the gasoline or its vapors would cause the non-polar polymeric material of the detector to swell, change resistance, etc. (depending on what type of detector was used) and correspondingly trip an alarm.
- gasoline a non-polar liquid
- change resistance etc.
- EXAMPLE 1 A 4 mil Kapton ® film (a polyimide support film supplied by Dupont) was bar coated with 12 mils of Electrodag ® 502 (carbon filled fluoroelastomer dissolved in methyl ethyl ketone supplied by Acheson Colloids Inc.) and allowed to air dry. The final coating of Electrodag ® 502 had a thickness of about 0.4 mil and a specific resistivity of 1 Kohm/sq. The coated film was then cut into 1 inch squares and fine copper (Cu) wires were bonded to the edges of the cut film using a silver epoxy resin as the adhesive (Epotek ® E3114 supplied by Epoxy Technology Inc.).
- Electrodag ® 502 carbon filled fluoroelastomer dissolved in methyl ethyl ketone supplied by Acheson Colloids Inc.
- the coated film was then cut into 1 inch squares and fine copper (Cu) wires were bonded to the edges of the cut film using a silver epoxy resin as the adhesive
- EXAMPLE 2 A 4 mil polyester film was bar coated with 14 mils of a 50:50 mixture of Electrodag ® 501 (Acheson Colloids Inc.): PLV 2069 Viton ® (Pelomer Labs) solution and was dried at 60°C for 30 minutes. The dry film thickness of the coating was about 0.7 mils. Next, a 0.62 x 0.20 inch rectangular section of the coated polyester film was cut out and was electrically bonded at the longest distance edges with wires using an Ag epoxy (Epotek ® E3114 supplied by Epoxy Technology Inc.). The normal resistance of the device was 40-50 Kohms. When exposed to IM LiPF 6 EC:DMC 1 :1 Lilon electrolyte vapor, the resistance increased to 130 Kohms in one minute and greater than 1 mega-ohm in less than two minutes.
- IM LiPF 6 EC:DMC 1 :1 Lilon electrolyte vapor the resistance increased to 130 Kohms in one minute and greater than 1 mega-
- the carbon black, graphite and Tamol 165 were predispersed in the solvent with a ball mill followed by the addition of the urethane polymer solution. After the cast film was dried, 0.62 x 0.20 inch rectangular sections were cut and electrical leads were Ag epoxied to the longest edges using Epotek ® E3114 (Epoxy Technology Inc.) and heat cured at 130°C for about 30 minutes. The resistance of the device, as measured by a standard ohm meter, was 27 Kohm. When exposed to IM LiPF 6 ethylene carbonate: dimethyl carbonate 1 : 1 vapor, the resistance rose to 70 Kohm in about 1 minute.
- EXAMPLE 4 An acrylic matrix film was prepared by mixing the following acrylic polymer solution:
- a 14 mil wet drawdown was cast onto a 4 mil polyester support film and dried, resulting in a 3 mil dry acrylic/carbon coating.
- Gelva 2480 crosslinks after it is dried rendering it insoluble but swellable in solvents.
- Rectangular sections (0.62 X 0.20 inch) were cut and electrical leads were silver/epoxied to the longest edges using Epotek ® E3114 (Epoxy Technology Inc.) and heat cured at 130°C for about 30 minutes.
- the film was attached to a multiohmeter and the resistance was recorded. The resistance of the device was 10 Kohm. When exposed to IM LiPF 6 ethylene carbonate: dimethyl carbonate 1:1 vapor, the resistance of the device rose to 28 Kohms in 2 minutes and 380 Kohm in 15 minutes.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Analytical Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Combustion & Propulsion (AREA)
- Food Science & Technology (AREA)
- Medicinal Chemistry (AREA)
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
- Hybrid Cells (AREA)
Abstract
The present invention is directed to an organic liquid and/or vapor detector which is useful in Lithium Ion batteries and other devices containing organic liquids and/or vapors comprising a supported or unsupported swellable polymeric material which is sensitive to organic liquids and/or vapors. The swellable polymeric material is a polymer, copolymer or physical mixture thereof that may, optionally, be filled with electrically conductive particles. A process of preparing the detector and devices containing the same are also disclosed.
Description
ORGANIC SOLVENT VAPOR DETECTOR The present invention relates generally to the art of an organic liquid and/or vapor detector and more specifically to a battery pack detector which can be used in conjunction with a battery operated device or an intelligent on-board battery controller. The detector of the present invention comprises an organic liquid swellable polymeric material which, optionally, may contain electrically conductive particles dispersed therein. The detector of the present invention, which may be supported or unsupported, is highly sensitive in detecting organic liquids and/or vapors typically found in rechargeable or primary batteries as well as the level of such organic liquids in a container.
The advent of intelligent portable electronic devices such as notebook computers, video cameras, cellular phones and the like has enabled the development of rechargeable and primary batteries that maintain safety and in some instances, can communicate with the intelligent device to provide accurate information on the battery's present state of charge, and how best to recharge the battery to maintain maximum battery life, thus enabling the highest number of charge-discharge states. A user of such intelligent portable electronic devices, using such batteries, will not only know how much charge is left in the battery, but battery run time at various rates of power consumption. This enables the user to select a mode of operation that will enable maximum service life on the remaining state of charge and, how long the device will operate.
Although rechargeable and primary batteries are reliable and an economical energy source, under some circumstances such as during various charge- discharge cycles, leaks in the battery may develop which could adversely affect the operation of the electronics and safety devices. The leaks are typically caused by either defects in the construction of the battery itself or by generation of electrolytic gases during battery cycling or elevated temperature storage that may rupture the battery cell or cause a seal failure. Even though leaks are not a common occurrence in rechargeable and primary batteries, they can be detrimental to the electronic safety circuitry of the portable device since the battery is typically in close proximity to the
device's electronic circuitry. There is thus a need for a battery pack containing a leak detector which is highly responsive to organic liquids and/or vapors that are present in the battery's cell. The electronics, upon sensing the leak, would have sufficient time to render the pack benign. By maintaining safety, the pack could be returned for repair, replacement or etc. The user could also be signaled that the pack had suffered fatal damage and should be replaced or repaired.
Accordingly, one object of the present invention is to provide a detector that can be used in a battery pack or in conjunction with an intelligent portable electronic device. Another object of the present invention is to provide a detector which is highly sensitive to polar and/or non-polar organic liquids and/or vapors and thus provides a rapid response if such organic liquids and/or vapors are emitted by a nearby battery cell or other source containing such organic liquids and/or vapors.
A further object of the present invention is to provide a detector which can be used to detect leaks in various devices and/or the fluid level of an organic liquid in a container.
Another object of the invention is to provide a reversible response. That is, the detector is capable of signaling the removal of organic liquid and/or vapor from a container. These as well as other objects are achieved by the present invention by providing a detector which comprises a supported or unsupported organic liquid swellable polymeric material which, optionally, may contain electrically conductive particles dispersed therein. That is, the detector of the present invention comprises a swellable polymeric material which is capable of exhibiting volume changes when exposed to an organic liquid and/or vapor.
Any change in the volume of the polymeric material as a result of liquid swelling, can subsequently produce an electrical signal response such as a change in resistivity, capacitance or transducer acoustical inductance. The nature of the polymeric material is dependent upon the solubility parameters such as polarity and hydrogen bonding index of the target liquid. Generally, the solubility parameters of the polymeric material is similar to the target liquid. Thus, when detection of polar liquids and/or vapors is sought, the polymeric material is composed of a polar
swellable polymeric material. Likewise, a non-polar swellable polymeric material is used for detecting non-polar organic liquids and/or vapors.
When operating in the preferred resistance mode, the polymeric material is filled with electrically conductive particles and electrically bonded between electrically conductive terminals. The polymeric material can be coated onto at least one side of a mechanically supporting carrier, or it can be unsupported. Organic liquid swelling of the polymeric material increases the distance between the dispersed electrically conductive particles resulting in a corresponding electrical resistance increase. The preferred geometry of the polymeric material operating in the resistive mode is a supported or unsupported thin film. The rate of change of the electrical signal response is proportional to the rate of swelling of the polymeric material. In order to maximize the response time, the mass ratio of the polymeric material to target organic liquid or vapor must be minimized and this can be achieved with thin film geometry.
In another embodiment of the present invention, the polymeric material can be operated in the capacitive mode and is achieved by sandwiching the polymeric material, preferably as a thin film, between two electrically conductive porous or nonporous plates. Exposure to an organic liquid and/or vapor induces swelling of the polymeric material and produces a corresponding change in the distance between the conductive plates resulting in a capacitive signal.
In yet another embodiment of the present invention, the polymeric material can be operated in an acoustical conductive mode by mechanically attaching the polymeric material between two mechanical transducers (a transmitter and receiver), such as is present in a surface acoustical wave (SAW) device. Exposure to an organic liquid and/or vapor produces a change in the acoustical conduction properties of the swollen polymeric material resulting in a corresponding modulation of the transducer signal.
Another aspect of the present invention relates to processes of fabricating the aforementioned detector. In accordance with this aspect of the present invention, the detector is fabricated by either printing the swellable polymeric material using printing techniques well known to those skilled in the art directly across two
electrically conductive circuit traces on a printed circuit board, or as a separate supported film component which is subsequently electrically connected to a circuit. An example of the latter method is as follows: providing the above mentioned polymeric material coated support film; diecutting said polymeric coated support film to provide a material having a resistance of from about 100 to about 1 Megohms/sq.; and attaching electrically conductive wires to said diecut film or directly bonding the diecut film to a circuit board.
A further aspect of the present invention relates to various devices such as smoke detectors, fire alarms and battery packs for camcorders and the like which contain the detector of the present invention. In the case of battery packs, there is provided a terminal means for connecting the battery pack to a battery powered device, a battery including at least one rechargeable or primary battery cell connected to said terminal means, and the detector of the present invention connected to the battery. This set-up allows for the detection of leaks by the nearby battery cell.
In yet another aspect of the present invention, the detector is utilized as a continuous level indicator to monitor the amount of fluid in a container. This aspect of the present invention is predicated on the ability of the polymeric material to return to substantially the same form as prior to liquid contact. Figure 1 is a cross-sectional view of a detector of the present invention comprising an unfilled organic liquid and/or vapor swellable polymeric material which is sandwiched between two electrically conductive plates.
Figure 2 is a cross-sectional view of a detector of the present invention comprising an electrically conductive filled organic liquid and/or vapor swellable polymeric material supported on a polymer base.
Figure 3 is an electronic diagram showing the detector of the present invention in use in a Duracell Battery Operating System (hereinafter 'DBOS').
As stated above, the detector of the present invention comprises an organic liquid and/or vapor swellable polymeric material that, optionally, may be filled with electrically conductive particles. By "swellable polymeric material" it is meant any polymer, copolymer or physical mixture thereof which upon contact with an organic liquid and/or vapor exhibits volume expansion. It is noted that after the
organic liquid and/or vapor is removed, the polymeric material returns to its original volume.
The detector of the present invention may be in any geometric form or shape such as cubic, spherical or thin film. A preferred geometric form of the detector of the present invention is a thin film. As stated above, the detector of the present invention may be supported on a carrier material or it may be unsupported depending upon its mode of operation.
Reference is now made to the accompanying drawings which show the various detectors of the present invention. It is emphasized that like elements in the drawings are referred to by like reference numerals. Specifically, in Fig. 1, there is shown a capacitive detector 10 which comprises an organic liquid and/or vapor swellable polymeric material 14 that is sandwiched between conductive plates 16 and 16'. Conductive plates 16 and 16' employed in the present invention are composed of conventional conductive materials such as Cu, Ag, brass, Sn, Ni, Au and the like. In this embodiment, polymeric material 14 is not filled with an electrically conductive material. If plates 16 and 16' are replaced with a transmitting and receiving mechanical transducer, the device operates as an acoustical transducer type organic liquid detector.
In another embodiment of the present invention, as shown in Fig. 2, detector 10 is a solid material comprising a support film 12 which is coated with an organic liquid and/or vapor swellable polymeric material 14 that is filled with electrically conductive particles. Alternatively, support film 12 may be a printed circuit board or card wherein the filled organic liquid and/or vapor swellable polymeric material is coated or printed oh the surface thereof. Support film 12 that is employed in the present invention as a carrier material may be any non-electrically conductive material that is not dissolved or the integrity of which is not adversely affected by the matrix coating solvent. Preferred materials are polymer films, sheets or laminates such as polyesters (including poly(ethylene terephthalate), poly(butylene terephthalate), poly (naphthelene terephthalate), aromatic heterocyclic polyimides (such as Kapton® supplied by Dupont), polypropylene, polyethylene, polyethylene ionomers (such as Surlyn® supplied by Dupont), polybutylene, polyvinyl fluoride, polyvinylidene chloride, polyvinyl chloride,
polyamides (such as Nylon® supplied by Dupont), ethylene vinylacetate, cellulose acetate, polyurethane and the like. As stated above, support film 12 may be a printed circuit board or card.
The thickness of the support film is not a critical limitation to the instant invention, but typically, the support film has a thickness which ranges from about 0.5 to about 50 mils.
Polymeric material 14 employed in the present invention is any polar or non-polar elastomeric polymer or copolymer that is preferably crosslinked and which swells upon contact with an organic liquid and/or vapor. Physical mixtures of said polymers and/or copolymers are also contemplated by the instant invention. The term "physical mixtures" is used herein to denote an admixture of polymers and/or copolymers wherein no chemical bonding between said polymers and/or copolymers is formed. Additionally it is preferred, but not necessary, that the swellable polymeric material has a glass transition temperature below about 30°C in order to have the polymer chains mobile enough to expand upon contact with an organic liquid and/or vapor.
Suitable polymers that may be used in forming polymeric material 14 include, but are not limited to: fiuoroelastomers, urethanes, neoprenes, polyacrylates, polysulfides, silicones, butyl and the like. Examples of suitable copolymers that may be employed include, but ar not limited to: acrylonitrile-butadiene, acrylonitrile- styrene-butadiene, acrylonitrile-styrene-isoprene, styrene-butadiene, styrene-butadiene- isoprene and the like. A highly preferred polymer employed in the present invention is a flouroelastomer such as is commercially available from Pelomer Labs under the tradename PLV 2069. It is emphasized that the above mentioned polymers and copolymers are highly sensitive to detecting polar or non-polar organic liquids and/or vapors depending on matching the respective polarity of the swellable polymer to the target organic liquid and/or vapor.
When organic liquid and/or vapor swellable polymeric material 14 is filled, it is typically filled with a population of electrically conductive particles. The electrically conductive particles employed in the present invention are conventional conductors well known to those skilled in the art. Examples of electrically conductive
particles that may be employed in the present invention include, but are not limited to: carbon black, graphite, silver, tin, gold, palladium, nickel and the like. Mixtures of these electrically conductive particles such as silver and graphite are also contemplated herein. Highly preferred electrically conductive particles that are employed in the present invention are a mixture of carbon black and graphite.
The electrically conductive particles may be any shape. It is however preferred that the electrically conductive particles are flat shaped flakes or spherical-shaped powders. Typically, the size of the electrically conductive particles range from about 10 nm to about 100 microns. More preferably, the particle size of the electrically conductive particles is from about 0.01 to about 50 microns.
It should be emphasized that the unfilled swellable polymeric material or the electrically conductive filled swellable polymeric material employed in the present invention may be fabricated using conventional means well known to those skilled in the art or they can be commercially obtained. An example of a commercially available electrically conductive filled swellable polymeric material is Electrodag 501® supplied by Acheson Colloids Inc. which is a combination of carbon black and graphite particles in a fluoroelastomer resin system.
Typically, the organic liquid and/or vapor swellable polymeric material contains from about 1 to about 90%, by weight, of electrically conductive particles dispersed in the matrix of the polymeric material. More preferably, the swellable polymeric material contains from about 30 to about 70%, by weight, of electrically conductive particles.
When supported on a base material, the organic liquid and/or vapor swellable polymeric material is in the form of a thin coating which is prepared by predispersing the conductive particles in a solvent capable of dissolving the swellable polymeric material, followed by dissolving the swellable polymeric material. Depending on the type of swellable polymeric material employed, suitable coating solvents include, but are not limited to: methyl ethyl ketone, acetone, toluene, tetrahydrofuran and the like. Alternatively, the matrix coating solution can be prepared by mixing commercially available conductive coating solutions with suitable swellable polymeric materials.
Following application to the support film, the electrically conductive
filled swellable polymeric material has a resistance of from about 20 ohm/sq. to about 1 Megohm/sq. More preferably, the resistance of the electrically conductive filled swellable polymeric material, prior to application, is from about 1 Kohm/sq to about 100 Kohm/sq and can be adjusted by varying the ratio of conductive particle mass to swellable polymeric mass.
The filled swellable polymeric solution is cast upon, i.e. applied to at least one surface of support film 12, using conventional coating techniques well known to those skilled in the art. For example, coating of the support film with the filled swellable polymeric material may be conducted by brushing, dipping, knife coating, gravure, wire bar coating, spraying and the like. A preferred means of applying the filled swellable polymeric coating solution to the support film is by wire bar coating. It is again emphasized that when the support material is a circuit board or card, the swellable polymeric material containing electrically conductive particles is either printed directly on to the circuit elements of the circuit board or card using printing techniques well known to those skilled in the art or, alternatively, it is first supported on a support film and then bonded to the circuitry found on the circuit board or card using a silver epoxy adhesive.
In accordance with the present invention, a uniform coating of the filled swellable polymeric solution is applied to the surface of the support film. By "uniform", it is meant that the wet coating has a thickness of from about 1 to about 30 mils. It is emphasized that the above range represents the thickness of the wet coating prior to drying.
Next, the coated support film is dried using conditions and techniques well known to those skilled in the art. One way of drying the coated film is by air drying, which, depending upon the size of the coated film and the coating solvent chosen, may take from about 0.1 to about 1.0 hrs. Another way of drying the coated film is by heating in an oven. Typically, when oven drying is employed, the temperature of the oven is from about 60° to about 150°C and the drying time is from about 1 to about 30 minutes. No matter which of the above drying techniques is employed, the final thickness of the coating is from about 0.1 to about 1.5 mils.
After drying, the coated support film is diecut to a shape which provides a resistance of from about 20 ohms/sq to about 1 Megohm/sq. Moreover, since the
polymeric swelling rate is proportional to the rate of increase in the organic liquid/polymeric mass ratio, the ideal shape of the device would be a thin film.
All of the above mentioned properties can be achieved by diecutting the coated film into a shape that maximizes the electrical path length while minimizing the overall outer dimensions, such as a "u" or "w" shaped thin film.
The next step of the present invention is to attach electrical conductive wires 20, e.g. Ag or Cu wires, to the diecut coated film. The wires can be attached at any edge of the thin film but it is preferred they be attached at the most distant ends of the coated surface of the thin film. The wires are attached using conventional electrical bonding means well known to those skilled in the art. A preferred means of electrically bonding wires 20 to the diecut film is by using a silver epoxy filled thermoplastic or thermoset adhesive 18 such as a silver epoxy.
When the organic liquid and/or vapor swellable polymeric material is not supported on a support film, the swellable polymeric material is either positioned between two conductive plates or two transducers which are electrically connected to a circuit. In these cases, the swellable polymeric material is in the form of an unsupport thin film and is diecut as mentioned above and placed between the plates or transducers.
The above description describes the basic form of the detector of the present invention as well as the process which is employed for fabricating the same. The detector of the present invention is useful in detecting organic liquids, e.g., polar and/or non-polar liquids, emitted or leaked by a nearby source containing said organic liquids. Alternatively, the detector of the present invention can be used to continuously monitor the level of an organic liquid in a container. The following description illustrates the use of the detector of the present invention as a leak detector in a battery pack which comprises at least one rechargeable or primary battery cell which contains a polar organic liquid as the electrolyte. Suitable polar organic liquids which may be present in such battery cells and thus detected by the present invention are ethylene carbonate, dimethyl carbonate, and the like. Mixtures of these polar organic liquids may also be present in the battery cell.
The term "rechargeable battery cell" is used herein to denote
rechargeable Lithium Ion (Lilon), Nickel Metal Hydride (NiMH) or Nickel Cadmium (NiCad) batteries. A preferred rechargeable battery employed in the present invention is a Lilon battery.
In accordance with the present invention, a battery pack for detecting polar organic liquids and/or vapors is provided which comprises terminal means for connecting the pack to a battery powered device, a battery including at least one of the aforementioned rechargeable battery cells connected to said terminal means, and a detector of the present invention electrically connected to said battery. The rechargeable battery cell may be replaced by a primary battery cell which is described for example in Kirk-Othmer, Encyclopedia of Chemical Technology, Third Edition, Vol. 13, 1978, pp. 503-545.
When a leak in the battery cell is detected by the above arrangement, an electronic signal is emitted by the leak detector to a computer, fuse or other device which will alarm the user of such a leak. A preferred device for alarming the user of a leak is a smart battery device, such as a Duracell Battery Operating System (DBOS) which includes ASIC (Application Specific Integrated Circuit) hardware, CPU, Analog to Digital Converter, Current Measurement Means, Temperature Measurement Means, Pack- Voltage Measurement Means, Cell Voltage Measurement Means, ROM, RAM, RAM Data Back-Up Circuit, 12C/SMBUS Interface, Clock generator circuit, Wake-up comparator circuit, LED Drivers, Interface Circuits, Hardware Modes of operation, Run Mode: Entry/Exit, Sample Mode: Entry/Exit and Sleep Mode: Entry/Exit. A complete discussion of DBOS can be found in commonly owned applications U.S. Serial Nos. 08/336,945, filed November 10, 1994, now U.S. Patent No. 5,633,573; and 08/318,004 filed October 4, 1994, now U.S. Patent No. 5,606,242; as well as copending and commonly owned U.S. provisional application Serial No. 60/034,320, filed December 20, 1996, (Attorney docket P- 10445) the contents of which are incorporated herein by reference.
Reference is made to Fig. 3 which shows the use of a detector of the present invention comprising a supported swellable polymeric material which is filled with electrically conductive particles in a typical DBOS module. In this figure, Cl, C2 and C3 denote Lilon cells which are connected in series with each other; Ql and Q2 are transistors which are connected to the Lilon cells through resistor R5; FI is a fuse;
Rl and VI are the resistance and the voltage between the positive and negative terminal ends, respectively. The detector of the present invention is also positioned between the positive and negative terminal ends of the DBOS module. The module has two major functional blocks, namely overvoltage protection and fuel gauging whose functions are described in more detail in the aforementioned copending applications. It also contains an electronic switch circuit and data communication ports, I2C and port, respectively, which are typically connected to a computer.
In accordance with the present invention, when the detector of the present invention is exposed to a polar organic liquid and/or vapor, its electrical resistance rises increasing the voltage VI. The electronic switch circuit shown in Fig. 3 is designed to trip in response to increasing voltage such that it provides a low resistance path and blows fuse FI.
In addition to being employed for detecting leaks in batteries, the detector or the present invention may be employed in other areas wherein organic liquids (polar and/or non-polar) and/or vapors are emitted into the atmosphere.
Examples of other uses for the detector of the present invention include, but are not limited to: solvent storage areas, naval bilge compartments, chemical vapor hoods, fire alarms, smoke stacks, car engine compartments, solvent coating manufacturing operations and the like. For example, when used in a boat bilge, if gasoline (a non-polar liquid) were to leak from an adjacent fuel tank, the gasoline or its vapors would cause the non-polar polymeric material of the detector to swell, change resistance, etc. (depending on what type of detector was used) and correspondingly trip an alarm. The following examples are given to illustrate the scope of the invention. Because these examples are given for illustrative purposes only, the invention embodied therein should not be limited thereto.
EXAMPLE 1 A 4 mil Kapton® film (a polyimide support film supplied by Dupont) was bar coated with 12 mils of Electrodag® 502 (carbon filled fluoroelastomer dissolved in methyl ethyl ketone supplied by Acheson Colloids Inc.) and allowed to air dry. The final coating of Electrodag® 502 had a thickness of about 0.4 mil and a specific resistivity of 1 Kohm/sq. The coated film was then cut into 1 inch squares
and fine copper (Cu) wires were bonded to the edges of the cut film using a silver epoxy resin as the adhesive (Epotek® E3114 supplied by Epoxy Technology Inc.). When exposed to IM LiPF6 EC (ethylene carbonate): DMC (dimethyl carbonate) lithium ion cell electrolyte vapor (100% saturated in vapor phase), the resistivity increases by a factor of over two times within sixty seconds. This example demonstrates that a support film coated with an electrically conductive filled swellable polymeric material can be successfully used as a leak detector in lithium ion batteries.
EXAMPLE 2 A 4 mil polyester film was bar coated with 14 mils of a 50:50 mixture of Electrodag® 501 (Acheson Colloids Inc.): PLV 2069 Viton® (Pelomer Labs) solution and was dried at 60°C for 30 minutes. The dry film thickness of the coating was about 0.7 mils. Next, a 0.62 x 0.20 inch rectangular section of the coated polyester film was cut out and was electrically bonded at the longest distance edges with wires using an Ag epoxy (Epotek® E3114 supplied by Epoxy Technology Inc.). The normal resistance of the device was 40-50 Kohms. When exposed to IM LiPF6 EC:DMC 1 :1 Lilon electrolyte vapor, the resistance increased to 130 Kohms in one minute and greater than 1 mega-ohm in less than two minutes.
EXAMPLE 3 A 7 mil wet drawdown of the following polymer solution was cast onto a 4 mil Mylar® support film (a polyester film supplied by DuPont):
The carbon black, graphite and Tamol 165 were predispersed in the
solvent with a ball mill followed by the addition of the urethane polymer solution. After the cast film was dried, 0.62 x 0.20 inch rectangular sections were cut and electrical leads were Ag epoxied to the longest edges using Epotek® E3114 (Epoxy Technology Inc.) and heat cured at 130°C for about 30 minutes. The resistance of the device, as measured by a standard ohm meter, was 27 Kohm. When exposed to IM LiPF6 ethylene carbonate: dimethyl carbonate 1 : 1 vapor, the resistance rose to 70 Kohm in about 1 minute.
EXAMPLE 4 An acrylic matrix film was prepared by mixing the following acrylic polymer solution:
A 14 mil wet drawdown was cast onto a 4 mil polyester support film and dried, resulting in a 3 mil dry acrylic/carbon coating. Gelva 2480 crosslinks after it is dried rendering it insoluble but swellable in solvents. Rectangular sections (0.62 X 0.20 inch) were cut and electrical leads were silver/epoxied to the longest edges using Epotek® E3114 (Epoxy Technology Inc.) and heat cured at 130°C for about 30 minutes. The film was attached to a multiohmeter and the resistance was recorded. The resistance of the device was 10 Kohm. When exposed to IM LiPF6 ethylene carbonate: dimethyl carbonate 1:1 vapor, the resistance of the device rose to 28 Kohms in 2 minutes and 380 Kohm in 15 minutes. The above embodiments and examples are given to illustrate the score and spirit of the present invention. These embodiments and examples will make apparent, to those skilled in the art, other embodiments and examples. These other embodiments and examples are within the contemplation of the present invention; therefore, the instant invention should be limited only by the appended claims.
Claims
C L A I M S 1. A detector comprising a swellable polymeric material, wherein said swellable polymeric material is a swellable polymer, copolymer or physical mixture thereof capable of volume changes when exposed to an organic liquid and/or vapor.
2. The detector of claim 1 , wherein said swellable polymeric material is filled with electrically conductive particles.
3. The detector of claim 1 or 2, wherein the swellable polymeric material is supported on a support film, circuit board or card.
4. The detector of claim 3, wherein the support material is a support film.
5. The detector of claim 2, wherein said electrically conductive particles are selected from the group consisting of carbon black, graphite, silver, tin, gold, palladium, nickel and mixtures thereof.
6. The detector of claim 5, wherein said electrically conductive particles are a mixture of carbon black and graphite particles.
7. The detector of claim 1, wherein said swellable polymeric material has a glass transitition temperature below about 30┬░C.
8. The detector of claim 1, wherein said swellable polymeric material is a crosslinked polymer or copolymer capable of undergoing organic liquid and/or vapor absorption and corresponding volumetric expansion.
9. The detector of claim 1, wherein said polymeric material is composed of a polar or non-polar polymer or copolymer.
10. The detector of claim 9, wherein said swellable polymeric material is a polymer selected from the group consisting of fluoroelastomers, urethanes, neoprenes, polyacrylates, polysulfides, butyl, silicones, and or physical mixtures thereof.
11. The detector of claim 9, wherein said copolymer is selected from the group consisting of acrylonitrile-styrene-butadiene, acrylonitrile-butadiene and styrene-isoprene, styrene-butadiene and styrene-butadiene-isoprene, butyl rubber, isoprene rubber and physical mixtures thereof.
12. The detector of claim 10, wherein said swellable polymeric material is a fluoroelastomer.
13. The detector of claim 2, wherein said electrically conductive particles are flat shaped flakes or spherical-shaped powders.
14. The detector of claim 2, wherein said electrically conductive particles have a particle size ranging from about 10 run to 100 microns.
15. The detector of claim 14, wherein said electrically conductive particles have a particle size of from about 0.01 to about 50 microns.
16. The detector of claim 4, wherein said support film has a thickness of from about 0.5 to about 50 mils.
17. The detector of claim 2, wherein said swellable polymeric material contains from about 1 to about 90%, by weight, of said electrically conductive particles.
18. The detector of claim 1, wherein said swellable polymeric material is applied to a support material as a uniform wet thin film having a thickness of from about 1 to about 30 mils.
19. The detector of claim 18, wherein said swellable polymeric material, after drying, has a thickness of from about 0.1 to about 1.5 mils.
20. The detector of claim 1, wherein said swellable polymeric material is unsupported and is positioned between two porous or non-porous electrically conductive plates.
21. The detector of claim 1, wherein said swellable polymeric material is unsupported and is positioned between a transmitting and receiving mechanical transducer.
22. A detector useful in battery packs comprising: a swellable polymeric material which swells when contacted with a polar organic liquid and/or vapor.
23. The detector of claim 22, wherein said swellable polymeric material is a polar polymer copolymer, or physical mixture thereof.
24. The detector of claim 22, wherein said swellable polymeric material is filled with electrically conductive particles.
25. A process of fabricating an organic liquid and/or vapor detector useful in battery packs comprising: providing a support film having an organic liquid and/or vapor swellable polymeric material coated on at least one surface of said base material; and diecutting said coated support film to provide a material having an electrical resistance of from about 20 ohms to about 1 Megohm/sq.
26. The process of claim 25, wherein said swellable polymeric material is a polymer, copolymer or physical mixture thereof capable of exhibiting a volume change when exposed to an organic liquid and/or vapor.
27. The process of claim 26, wherein said polymeric material is filled with electrically conductive particles.
28. The process of claim 25, further comprising attaching electrically conductive wires to said diecut film.
29. The process of claim 25, further comprising directly bonding the diecut film to a circuit board or card.
30. The process of claim 25, wherein said coating is applied by brushing, dipping, knife coating, grauve, wire bar coating or spraying.
31. The process of claim 30, wherein said coating is applied by wire bar coating.
32. The process of claim 28, wherein said electrically conductive wire is a
Cu or Ag wire.
33. The process of claim 32, wherein said wire is attached using a Ag epoxy adhesive.
34. The process of claim 25, wherein said diecut film is bonded to a circuit board or card using a Ag epoxy adhesive.
35. A process of providing a detector to a circuit board or card comprising providing a circuit board or card having circuit elements thereon; and printing a swellable polymeric material on said circuit elements.
36. The process of claim 35, wherein said swellable polymeric material is a polymer, copolymer or physical mixture thereof capable of exhibiting a volume change when exposed to an organic liquid and/or vapor.
37. The process of claim 36, wherein said swellable polymeric material is filled with electrically conductive particles.
38. A battery pack comprising: terminal means for connecting a battery pack to a battery powered device; a battery including at least one rechargeable or primary battery cell connected to said terminal means, and a detector according to claim 1 or 22 connected to said battery.
39. The battery pack of claim 38, wherein said rechargeable battery cell is a lithium ion battery cell.
40. The battery pack of claim 38, wherein said battery powered device is a notebook computer, a video camera or a cellular phone.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002294889A CA2294889A1 (en) | 1997-07-02 | 1998-06-26 | Organic solvent vapor detector |
| JP50723099A JP2002509609A (en) | 1997-07-02 | 1998-06-26 | Organic solvent vapor detector |
| AU79868/98A AU7986898A (en) | 1997-07-02 | 1998-06-26 | Organic solvent vapor detector |
| EP98930485A EP0993597A1 (en) | 1997-07-02 | 1998-06-26 | Organic solvent vapor detector |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US88738797A | 1997-07-02 | 1997-07-02 | |
| US08/887,387 | 1997-07-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1999001733A1 true WO1999001733A1 (en) | 1999-01-14 |
Family
ID=25391036
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US1998/013121 WO1999001733A1 (en) | 1997-07-02 | 1998-06-26 | Organic solvent vapor detector |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0993597A1 (en) |
| JP (1) | JP2002509609A (en) |
| AR (1) | AR013641A1 (en) |
| AU (1) | AU7986898A (en) |
| CA (1) | CA2294889A1 (en) |
| TW (1) | TW507067B (en) |
| WO (1) | WO1999001733A1 (en) |
| ZA (1) | ZA985775B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001025772A1 (en) * | 1999-10-06 | 2001-04-12 | Iowa State University Research Foundation, Inc. | Chemical sensor and coating for same |
| JP2002214179A (en) * | 2001-01-23 | 2002-07-31 | Fis Kk | Gas sensor |
| WO2003004976A2 (en) * | 2001-07-06 | 2003-01-16 | Moletherm Holding Ag | Sensor |
| US8252237B2 (en) | 2007-01-12 | 2012-08-28 | Nitto Denko Corporation | Substance detection sensor |
| CN107238646A (en) * | 2016-03-28 | 2017-10-10 | Tdk株式会社 | Detector and the electrochemical element for possessing detector |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7112304B2 (en) * | 2003-04-11 | 2006-09-26 | Therm-O-Disc, Incorporated | Robust chemiresistor sensor |
| KR100519767B1 (en) | 2003-04-11 | 2005-10-10 | 삼성에스디아이 주식회사 | Fuel amount control system comprising pressure sensor |
| JP2016148589A (en) * | 2015-02-12 | 2016-08-18 | セイコーエプソン株式会社 | Gel for sensor and sensor |
| US20240151673A1 (en) * | 2021-03-19 | 2024-05-09 | Panasonic Intellectual Property Management Co., Ltd. | Sensitive membrane and gas sensor |
Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4125822A (en) * | 1972-10-23 | 1978-11-14 | Benno Perren | Probe for determining organic liquids |
| JPS5769277A (en) * | 1980-10-17 | 1982-04-27 | Citizen Watch Co Ltd | Electronic watch with function of detecting liquid leakage of battery |
| JPS57174872A (en) * | 1981-04-17 | 1982-10-27 | Matsushita Electric Ind Co Ltd | Test method for closed alkali storage battery |
| GB2164200A (en) * | 1984-09-06 | 1986-03-12 | Tadiran Ltd | Leakage detection |
| US4605923A (en) * | 1984-11-02 | 1986-08-12 | Ensco, Inc. | Method and apparatus for detection of organic fluids |
| US4948683A (en) * | 1989-07-31 | 1990-08-14 | Honeywell Inc. | Reserve activated electrochemical cell with a cell condition checking apparatus |
| WO1991003734A1 (en) * | 1989-08-29 | 1991-03-21 | At & S Austria Technologie & System Technik Gesellschaft M.B.H. | Use of a swellable plastic and process for making a resistive moisture sensor |
| JPH0396846A (en) * | 1989-09-08 | 1991-04-22 | Mitsubishi Cable Ind Ltd | Low molecular weight organic liquid detecting sensor |
| JPH05109436A (en) * | 1991-10-15 | 1993-04-30 | Matsushita Electric Ind Co Ltd | Method of detecting liquid leaking from battery |
| JPH05326032A (en) * | 1992-05-26 | 1993-12-10 | Fujitsu Ltd | Battery abnormality detecting method |
| DE4220494A1 (en) * | 1992-06-23 | 1994-01-05 | Klaus Dr Ing Zahnert | Protective wrap for indicating battery electrolyte leakage in portable appts. - encloses cells with flexible spatial detector consisting of electrode foils, separated by insulator to contact escaping electrolyte before functional parts, and senses resistance drop |
| US5399445A (en) * | 1994-04-18 | 1995-03-21 | Aer Energy Resources | Battery case leakage detector |
| JPH08261969A (en) * | 1995-02-27 | 1996-10-11 | He Holdings Inc Dba Hughes Electron | Sensor for temporarily discharged material |
| JPH1012284A (en) * | 1996-06-21 | 1998-01-16 | Nippon Mori Energ Kk | Leakage detector for organic electrolyte battery |
| JPH10115569A (en) * | 1996-07-16 | 1998-05-06 | Samsung Electron Devices Co Ltd | Apparatus for sensing liquid leakage of secondary cell |
-
1998
- 1998-06-26 AU AU79868/98A patent/AU7986898A/en not_active Abandoned
- 1998-06-26 JP JP50723099A patent/JP2002509609A/en active Pending
- 1998-06-26 CA CA002294889A patent/CA2294889A1/en not_active Abandoned
- 1998-06-26 EP EP98930485A patent/EP0993597A1/en not_active Withdrawn
- 1998-06-26 WO PCT/US1998/013121 patent/WO1999001733A1/en not_active Application Discontinuation
- 1998-07-01 ZA ZA985775A patent/ZA985775B/en unknown
- 1998-07-01 AR ARP980103188A patent/AR013641A1/en unknown
- 1998-07-02 TW TW087110740A patent/TW507067B/en not_active IP Right Cessation
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4125822A (en) * | 1972-10-23 | 1978-11-14 | Benno Perren | Probe for determining organic liquids |
| JPS5769277A (en) * | 1980-10-17 | 1982-04-27 | Citizen Watch Co Ltd | Electronic watch with function of detecting liquid leakage of battery |
| JPS57174872A (en) * | 1981-04-17 | 1982-10-27 | Matsushita Electric Ind Co Ltd | Test method for closed alkali storage battery |
| GB2164200A (en) * | 1984-09-06 | 1986-03-12 | Tadiran Ltd | Leakage detection |
| US4605923A (en) * | 1984-11-02 | 1986-08-12 | Ensco, Inc. | Method and apparatus for detection of organic fluids |
| US4948683A (en) * | 1989-07-31 | 1990-08-14 | Honeywell Inc. | Reserve activated electrochemical cell with a cell condition checking apparatus |
| WO1991003734A1 (en) * | 1989-08-29 | 1991-03-21 | At & S Austria Technologie & System Technik Gesellschaft M.B.H. | Use of a swellable plastic and process for making a resistive moisture sensor |
| JPH0396846A (en) * | 1989-09-08 | 1991-04-22 | Mitsubishi Cable Ind Ltd | Low molecular weight organic liquid detecting sensor |
| JPH05109436A (en) * | 1991-10-15 | 1993-04-30 | Matsushita Electric Ind Co Ltd | Method of detecting liquid leaking from battery |
| JPH05326032A (en) * | 1992-05-26 | 1993-12-10 | Fujitsu Ltd | Battery abnormality detecting method |
| DE4220494A1 (en) * | 1992-06-23 | 1994-01-05 | Klaus Dr Ing Zahnert | Protective wrap for indicating battery electrolyte leakage in portable appts. - encloses cells with flexible spatial detector consisting of electrode foils, separated by insulator to contact escaping electrolyte before functional parts, and senses resistance drop |
| US5399445A (en) * | 1994-04-18 | 1995-03-21 | Aer Energy Resources | Battery case leakage detector |
| JPH08261969A (en) * | 1995-02-27 | 1996-10-11 | He Holdings Inc Dba Hughes Electron | Sensor for temporarily discharged material |
| JPH1012284A (en) * | 1996-06-21 | 1998-01-16 | Nippon Mori Energ Kk | Leakage detector for organic electrolyte battery |
| JPH10115569A (en) * | 1996-07-16 | 1998-05-06 | Samsung Electron Devices Co Ltd | Apparatus for sensing liquid leakage of secondary cell |
Non-Patent Citations (8)
| Title |
|---|
| DATABASE WPI Section EI Week 9828, Derwent World Patents Index; Class S02, AN 98-317409, XP002080623 * |
| PATENT ABSTRACTS OF JAPAN vol. 006, no. 148 (P - 133) 7 August 1982 (1982-08-07) * |
| PATENT ABSTRACTS OF JAPAN vol. 007, no. 017 (E - 154) 22 January 1983 (1983-01-22) * |
| PATENT ABSTRACTS OF JAPAN vol. 015, no. 281 (P - 1228) 17 July 1991 (1991-07-17) * |
| PATENT ABSTRACTS OF JAPAN vol. 017, no. 460 (E - 1419) 23 August 1993 (1993-08-23) * |
| PATENT ABSTRACTS OF JAPAN vol. 018, no. 139 (E - 1519) 8 March 1994 (1994-03-08) * |
| PATENT ABSTRACTS OF JAPAN vol. 098, no. 005 30 April 1998 (1998-04-30) * |
| PATENT ABSTRACTS OF JAPAN vol. 098, no. 007 31 March 1998 (1998-03-31) * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001025772A1 (en) * | 1999-10-06 | 2001-04-12 | Iowa State University Research Foundation, Inc. | Chemical sensor and coating for same |
| JP2002214179A (en) * | 2001-01-23 | 2002-07-31 | Fis Kk | Gas sensor |
| JP4653319B2 (en) * | 2001-01-23 | 2011-03-16 | エフアイエス株式会社 | Gas sensor |
| WO2003004976A2 (en) * | 2001-07-06 | 2003-01-16 | Moletherm Holding Ag | Sensor |
| WO2003004976A3 (en) * | 2001-07-06 | 2004-04-22 | Moletherm Holding Ag | Sensor |
| US8252237B2 (en) | 2007-01-12 | 2012-08-28 | Nitto Denko Corporation | Substance detection sensor |
| CN107238646A (en) * | 2016-03-28 | 2017-10-10 | Tdk株式会社 | Detector and the electrochemical element for possessing detector |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2002509609A (en) | 2002-03-26 |
| TW507067B (en) | 2002-10-21 |
| AR013641A1 (en) | 2001-01-10 |
| AU7986898A (en) | 1999-01-25 |
| EP0993597A1 (en) | 2000-04-19 |
| ZA985775B (en) | 1999-01-26 |
| CA2294889A1 (en) | 1999-01-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5339024A (en) | Battery with electrochemical tester | |
| US9136509B2 (en) | Battery cell with an integrated pouch metal foil terminal | |
| EP1749329B1 (en) | Safety element for battery and battery with the same | |
| US20150226810A1 (en) | Sensor arrangement, battery cell and energy system | |
| US20120133521A1 (en) | Fault detection and monitoring in batteries | |
| JPH1012284A (en) | Leakage detector for organic electrolyte battery | |
| EP0605599B1 (en) | Battery with electrochemical tester | |
| CN102265449B (en) | Immersion sensor to protect battery | |
| EP0993597A1 (en) | Organic solvent vapor detector | |
| KR20170019044A (en) | Battery Pack Comprising Tape Containing Thermochromic Dye | |
| JP3588343B2 (en) | Battery pack | |
| CN102088063A (en) | Secondary battery | |
| KR101487496B1 (en) | Method and apparatus for checking insulation of pouch type secondary battery | |
| Aihara et al. | Characteristics of a thin film lithium-ion battery using plasticized solid polymer electrolyte | |
| US20070190403A1 (en) | Device for detecting electrolyte overflow and energy storage device having the same | |
| JP6531388B2 (en) | Non-aqueous electrolyte secondary battery and method of evaluating gas generation amount in battery using the battery. | |
| KR20110053004A (en) | Apparatus and method for protecting battery pack by detecting electrolyte leakage | |
| TWM456590U (en) | Lithium ion battery temperature sensor | |
| MXPA00000095A (en) | Organic solvent vapor detector | |
| CN108511834A (en) | Monitoring device, power-supply device and electric vehicle | |
| KR102109224B1 (en) | System and method for monitoring battery case | |
| KR102669798B1 (en) | Apparatus for detecting the pressure of battery | |
| US20240142322A1 (en) | Battery Pressure Measuring Sensor and Battery Pressure Measuring Apparatus Including the Same | |
| JP2007250194A (en) | Short circuit detector for battery pack | |
| KR20210081611A (en) | A pouch for analyzing the swelling characteristics of the battery cells and methods of analyzing the battery cells using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AK | Designated states |
Kind code of ref document: A1 Designated state(s): AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DK EE ES FI GB GE GH GM GW HU ID IL IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG US UZ VN YU ZW |
|
| AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): GH GM KE LS MW SD SZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN ML MR NE SN TD TG |
|
| DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
| ENP | Entry into the national phase |
Ref document number: 2294889 Country of ref document: CA Ref country code: CA Ref document number: 2294889 Kind code of ref document: A Format of ref document f/p: F |
|
| NENP | Non-entry into the national phase |
Ref country code: KR |
|
| WWE | Wipo information: entry into national phase |
Ref document number: PA/a/2000/000095 Country of ref document: MX |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 1998930485 Country of ref document: EP |
|
| WWP | Wipo information: published in national office |
Ref document number: 1998930485 Country of ref document: EP |
|
| REG | Reference to national code |
Ref country code: DE Ref legal event code: 8642 |
|
| WWW | Wipo information: withdrawn in national office |
Ref document number: 1998930485 Country of ref document: EP |