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WO1997044838A1 - Electrolytes composites pour dispositifs electrochimiques - Google Patents

Electrolytes composites pour dispositifs electrochimiques Download PDF

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Publication number
WO1997044838A1
WO1997044838A1 PCT/US1996/007720 US9607720W WO9744838A1 WO 1997044838 A1 WO1997044838 A1 WO 1997044838A1 US 9607720 W US9607720 W US 9607720W WO 9744838 A1 WO9744838 A1 WO 9744838A1
Authority
WO
WIPO (PCT)
Prior art keywords
composite
matrix contains
matrix
plastic film
solid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US1996/007720
Other languages
English (en)
Inventor
Joseph Kejha
Stephen F. Hope
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lithium Technology Corp
Original Assignee
Lithium Technology Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lithium Technology Corp filed Critical Lithium Technology Corp
Priority to PCT/US1996/007720 priority Critical patent/WO1997044838A1/fr
Publication of WO1997044838A1 publication Critical patent/WO1997044838A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • 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

  • This invention relates to solid and semi-solid state electrolyte composites which contain an electrically insulating ribbon or sheet of expanded or perforated plastic which is coated with an ion conductive solid or semi-solid state matrix, and solidified by an alkali metal triflate salt, or an alkaline earth metal triflate salt and a radiation curable polymer.
  • the prior art polymer containing electrolytes also have exhibited poor adherence to the electrodes, are not flexible and do not possess sufficient mechanical strength to prevent shorting under pressure, or punching through of dendrites and consequent shorting of the device.
  • the composite electrolytes of the invention do not suffer from prior art problems and provide many positive advantages.
  • solid or semi-solid state electrolytes which are highly ion conductive, shorting- proof, dendrite-proof, flexible yet mechanically strong, lightweight, and inert to component materials, can be made by using a composite construction, where an electrically insulating material, preferably a ribbon or sheet of expanded or perforated plastic film, is coated with a liquid ion conductive material, which is solidified by using an alkali metal triflate salt, such as lithium triflate salt with polyethylene oxide (PEO) alone, or by an alkaline earth metal triflate salt with a radiation curable polymer to form a solid state ionically conductive matrix.
  • an electrically insulating material preferably a ribbon or sheet of expanded or perforated plastic film
  • a liquid ion conductive material which is solidified by using an alkali metal triflate salt, such as lithium triflate salt with polyethylene oxide (PEO) alone, or by an alkaline earth metal triflate salt with a radiation curable polymer to form a solid state
  • the principal object of the invention is to provide solid or semi-solid state composite electrolytes for batteries, capacitors and other electrochemical devices, which include an electrically insulating ribbon or sheet of lightweight expanded or perforated plastic film embedded in an ionically conductive matrix.
  • a further object of the invention is to provide composite electrolytes of the character aforesaid that are inert to the component materials used in various electrochemical devices . 44838 PC17US96/07720
  • a further object of the invention is to provide composite electrolytes of the character aforesaid that have excellent adherence and low shrinkage properties.
  • a further object of the invention is to provide composite electrolytes of the character aforesaid, that are flexible, tough and resistant to dendrite formation, easy to handle and lend themselves to mass production.
  • a further object of the invention is to provide composite electrolytes of the character aforesaid that are thinner than existing composite electrolytes and provide greater energy density.
  • a further object of the invention is to provide composite electrolytes of the character aforesaid that are lightweight, mechanically strong, and resist shorting under pressure.
  • a further object of the invention is to provide composite electrolytes of the character aforesaid that are highly stable at elevated temperatures, and allow rapid processing.
  • Fig. 1 is a diagrammatic view of an electrochemical device, such as a battery constructed in accordance with the invention
  • Fig. 2 is a vertical sectional view enlarged, taken approximately on the line 2-2 of Fig. 1
  • Electrochemical devices such as alkali or alkaline earth metal batteries, and for example lithium batteries, consist of at least an anode layer, a polymer electrolyte layer, and a cathode layer.
  • Such devices can be of virtually any desired size and configuration, and usually include additional layers such as current conducting backing layers, insulating layers and electrode connection layers.
  • the polymer dielectric or electrolyte layer must be compatible with the component materials used to fabricate the devices while possessing suitable ionic conductivity.
  • a base 11 which includes a web of material 11A, such as nickel foil or a ribbon of expanded or perforated metallized plastic film coated with a cathode material 12.
  • the cathodic material 12 is of well known type, and which may include finely ground particles of an intercalation compound such as vanadium oxide compound (V s Oi s ) / mixed with an organic solvent, polymer, alkali salt, and carbon black.
  • the cathode material 12 may then have an additional layer 14 of solid state polymeric electrolyte composite applied thereto, which composite may include an electrically non-conductive ribbon 15 of expanded plastic or perforated film material which is inert to the battery components and is preferably of polypropylene, but other materials such as polyethylene, polyester, ethylenetetra- fluoroethylene, polytetrafluoroethylene , polyvinylchloride, polyvinylfluoride and their variations are also suitable.
  • the ribbon 15 has a plurality of holes 16 therein which can be formed by punching, punching and expanding, or other suitable manufacturing methods.
  • the ribbon 15 can have up to approximately 90% (percent) air holes, dependent upon the material used and the requirements of the device.
  • the ribbon 15 can be of a thickness of .06 mil which is 1/25 of the thickness of an equivalent plastic fiber based ribbon (not shown) .
  • the ribbon 15 may also be of a punched and expanded or perforated porous plastic film membrane as shown in Fig. 2 such as Celguard of polypropylene, Teflon, polyethylene and other materials, made by Hoechst-Celanese Corp.
  • the ribbon 15 is coated with polymeric material 17, such as polyethylene oxide and an ester such as propylene carbonate (PC) , ethylene carbonate (EC), and dimethyl- carbonate (DMC) compounded with lithium trifluoromethane sulfonate, which is also referred to as lithium triflate.
  • An additional layer 18 of well known anode material is applied on top of the electrolyte layer.
  • a solid state polymeric electrolyte composition which is suitable, for example, for lithium batteries, capacitors, electrochemical devices, sensors, fuel cells, memory devices, and devices for brine electrolysis by an ion exchange method, contains propylene carbonate (PC) in the range of 10% to 90% by weight; 1,2 - dimethoxyethane (DME) in the range of 0.2% to 90% by weight; an ion conductive salt such as lithium triflate in the range of 1% to 90% by weight; and polyethylene oxide (PEO) in the range of 0.2% to 60% by weight.
  • PC propylene carbonate
  • DME 1,2 - dimethoxyethane
  • PEO polyethylene oxide
  • the PC can be replaced by any suitable ester, or ether or pyrrolidinone of the same percentage weight range.
  • the PC can also be replaced by a plurality of ion conductive esters, or a combination of esters, ethers and pyrrolidinones which provides improved conductivity and cyclability.
  • Suitable esters would be propylene carbonate, ethylene carbonate, butylene carbonate, dimethylcarbonate and diethylcarbonate.
  • Suitable ethers would be 1,2 - dimethoxypropane; 1,2 - dimethoxyethane; tetrahydrofuran; 2 - methyl tetrahydrofuran; and polyethylene glycol dimethyl ether.
  • a suitable pyrrolidinone would be 1,5 dimethyl - 2, pyrrolidinone; and n - methyl pyrrolidinone.
  • esters, ethers and pyrrolidinones can be substituted in the same total percentage weight range as the PC and/or DME they replace.
  • An additional alkali metal salt such as lithium hexafluorophosphate (LiPFJ may be added in the range of 0.1% to 50% (percent) by weight.
  • the described composition is heated to 70°C and the ribbon or sheet of expanded or perforated plastic film is dipped into the composition, coated and withdrawn, and then the composition is solidified by cooling it to 33°C or less, and by the presence of lithium triflate as described in prior U.S. Patent Application Serial No.
  • the lithium triflate salt should be replaced by a corresponding triflate salt to match the elected alkali or alkaline earth metal.
  • a sample of polymeric electrolyte composite was formed by compounding a lithium salt and a polymeric material which consisted of 42.75% (percent) by weight of propylene carbonate (PC) , 42.75% (percent) by weight of tetrahydrofuran (THF) , 11% (percent) by weight of lithium triflate and 3.5% (percent) by weight of polyethylene oxide (PEO) .
  • the mixture was heated to 70°C and became liquid, a ribbon of expanded polytetrafluoroethylene film was dipped into the hot liquid.
  • the hot coated ribbon was applied to an electrode layer, and by cooling it to 33°C or less, solidified due to the presence of the lithium- triflate and formed a solid or semi-solid, ion conductive layer of the desired thickness, strength and adherence.
  • polymeric electrolyte composite was formed by compounding a lithium salt and a polymeric material, which consisted of 36.6% (percent) by weight of PC, 36.6% (percent) by weight of DME, 10% (percent) by weight of lithium triflate, 1.8% (percent) by weight of PEO and 15% (percent) by weight of a radiation curable polymer such as Envibar UV-1244.
  • the mixture was heated to 70°C and became liquid, a ribbon of perforated polyethylene film was coated with the hot mixture.
  • the hot coated ribbon was applied to an electrode layer and exposed to ultraviolet radiation while still hot, which caused it to cross-link.
  • the composite was then cooled to 27°C or less and formed a solid or semi-solid ion conductive layer of desired thickness, strength and adherence.
  • polymeric electrolyte composite was formed by combining a lithium salt and a polymeric material, which consisted of 57% (percent) by weight of EC, 28.5% (percent) by weight of DMC, 11% (percent) by weight of lithium triflate, and 3.5% (percent) by weight of PEO.
  • polymeric electrolyte composite was formed by combining a lithium salt and a polymeric material, which consisted of 57% (percent) by weight of DMC, 28.5% (percent) by weight of EC, 11% (percent) by weight of lithium triflate, and 3.5% (percent) by weight of PEO.
  • the mixture was heated to 70°C and became liquid, a ribbon of expanded polypropylene film was coated with the hot mixture, and the hot coated ribbon was applied to an electrode layer.
  • the described composite was then cooled to 33°C or less and solidified due to the presence of lithium triflate and formed a solid or semi-solid ion conductive layer of desired thickness, strength and adherence.
  • EXAMPLE #5 Another example of polymeric electrolyte composite was formed by combining a lithium salt and a polymeric material, which consisted of 38.45 (percent) by weight of DMC, 38.45% (percent) by weight of EC, 9.9% (percent) by weight of lithium triflate, 9.0% (percent) by weight of lithiumhexafluorophosphate (LiPFJ , and 4.2% (percent) by weight of PEO.
  • the mixture was heated to 70°C and became liquid, a ribbon of expanded polyester film was coated with the hot mixture, and the hot coated ribbon was applied to an electrode layer.
  • the described composite was then cooled to 33°C or less and solidified due to the presence of lithium triflate and formed a solid or semi-solid ion conductive layer of desired thickness, strength and adherence.
  • polytetrafluoroethylene or ethylenetetrafluoroethylene are especially inert to battery chemistry and thus improve the battery cyclability.
  • the described polytetrafluoroethylene is also known under the trademark "Teflon”, and ethylenetetrafluoroethylene is known under the trademark "Tefzel”. It should be apparent that any other ion-conductive polymer matrices may be applied to the described expanded or perforated plastic films or sheets to obtain similar or equivalent composite electrolytes.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Dispersion Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Secondary Cells (AREA)
  • Primary Cells (AREA)

Abstract

On forme cet électrolyte composite (10) comprenant un polymère à l'état solide, selon un procédé consistant à revêtir un ruban (15) d'isolation électrique, inerte, ou une feuille d'un film plastique expansé ou perforé, à l'aide d'un polymère liquide (17) à conductance ionique, puis à faire durcir le polymère afin de former un électrolyte composite à l'état solide ou semi-solide.
PCT/US1996/007720 1996-05-24 1996-05-24 Electrolytes composites pour dispositifs electrochimiques Ceased WO1997044838A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/US1996/007720 WO1997044838A1 (fr) 1996-05-24 1996-05-24 Electrolytes composites pour dispositifs electrochimiques

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1996/007720 WO1997044838A1 (fr) 1996-05-24 1996-05-24 Electrolytes composites pour dispositifs electrochimiques

Publications (1)

Publication Number Publication Date
WO1997044838A1 true WO1997044838A1 (fr) 1997-11-27

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PCT/US1996/007720 Ceased WO1997044838A1 (fr) 1996-05-24 1996-05-24 Electrolytes composites pour dispositifs electrochimiques

Country Status (1)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000062364A1 (fr) * 1999-04-09 2000-10-19 Basf Aktiengesellschaft Corps composite utilisable comme batterie aux ions de lithium
WO2000062355A1 (fr) * 1999-04-09 2000-10-19 Basf Aktiengesellschaft Corps composites utilisables comme separateurs dans des cellules electrochimiques

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4618545A (en) * 1984-06-22 1986-10-21 Chloride Group Public Limited Company Recombination electric storage cells
US5051157A (en) * 1988-02-29 1991-09-24 University Of Victoria Spacer for an electrochemical apparatus
US5102752A (en) * 1990-08-16 1992-04-07 Hope Henry F Solid state composite electrolyte for batteries
US5372689A (en) * 1992-06-02 1994-12-13 United Technologies Corporation Dual-direction flow membrane support for water electrolyzers
US5378558A (en) * 1990-08-16 1995-01-03 Hope; Stephen F. Composite electrolytes for electrochemical devices

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4618545A (en) * 1984-06-22 1986-10-21 Chloride Group Public Limited Company Recombination electric storage cells
US5051157A (en) * 1988-02-29 1991-09-24 University Of Victoria Spacer for an electrochemical apparatus
US5102752A (en) * 1990-08-16 1992-04-07 Hope Henry F Solid state composite electrolyte for batteries
US5378558A (en) * 1990-08-16 1995-01-03 Hope; Stephen F. Composite electrolytes for electrochemical devices
US5372689A (en) * 1992-06-02 1994-12-13 United Technologies Corporation Dual-direction flow membrane support for water electrolyzers

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000062364A1 (fr) * 1999-04-09 2000-10-19 Basf Aktiengesellschaft Corps composite utilisable comme batterie aux ions de lithium
WO2000062355A1 (fr) * 1999-04-09 2000-10-19 Basf Aktiengesellschaft Corps composites utilisables comme separateurs dans des cellules electrochimiques
US6730440B1 (en) 1999-04-09 2004-05-04 Basf Aktiengesellschaft Composite body suitable for utilization as a lithium ion battery
US6746803B1 (en) 1999-04-09 2004-06-08 Basf Aktiengesellschaft Composite bodies used as separators in electrochemical cells

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