USH1462H - Solid state electrochemical lithium/polymer cell - Google Patents

Solid state electrochemical lithium/polymer cell Download PDF

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Publication number
USH1462H
USH1462H US08/153,948 US15394893A USH1462H US H1462 H USH1462 H US H1462H US 15394893 A US15394893 A US 15394893A US H1462 H USH1462 H US H1462H
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United States
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sub
lithium
cathode
solid state
poly
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US08/153,948
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Charles W. Walker, Jr.
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United States Department of the Army
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United States Department of the Army
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    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • 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 invention relates in general to lithium electrochemical cells and in particular to solid state electrochemical lithium/polymer cells that provide many cycles without a loss in capacity.
  • Li x CoO 2 Li x TiS 2
  • Li x Mn 2 O 4 Li x Mn 2 O 4 that provides many cycles without loss in capacity.
  • the absence of a liquid component would reduce or eliminate corrosion of the metallic lithium anode, as well as harmful chemical reactions at the cathode.
  • the general object of this invention is to provide an improved lithium electrochemical cell.
  • a more particular object of the invention is to provide such a cell that does not contain a liquid component that can cause corrosion of the metallic lithium anode as well as harmful chemical reactions at the cathode.
  • a still further object of the invention is to provide such a lithium electrochemical cell that allows for high cycle life and good capacity retention.
  • Another object of the invention is to provide such a lithium electrochemical cell that can be used as either a primary cell or a rechargeable cell.
  • Absence of a liquid component reduces or eliminates corrosion of the metallic lithium anode, as well as harmful chemical reactions at the cathode.
  • anions are intercalated rather than cations, with anion-doped polymer being electrically conductive, and undoped polymer being electrically resistive.
  • the polymer cathode is somewhat flexible, allowing anion doping and undoping to occur without structured damage, allowing for high cycle life and good capacity retention.
  • the use of the solid state lithium electrochemical cells as rechargeable cells allows for the development of thin film rechargeable mono and bipolar lithium cells.
  • the novel features of the cell include a system that is completely solid state.
  • polymers are employed as both cathode and electrolyte.
  • anions instead of lithium cations
  • the polymeric electrolyte and cathode components total only a few microns in thickness. This allows for the manufacture of a very thin, multicell, high voltage battery.
  • a solid electrolyte according to the invention includes a polymer host containing dissolved lithium salt, allowing the movement of Li + and X - ions between the electrodes.
  • ionically conducting polymers as for example (poly (ethylene oxide))
  • Solid polymer electrolyte (SPE) films can act both as a mechanical separator between the anode and cathode, and as a binder/adhesive to insure contact between electrodes. Elasticity allows the SPE to conform to electrode volume changes during cycling. Further, safety is enhanced in that there is no liquid electrolyte to leak from cells.
  • the SPE that can be used in the invention include at least one lithium salt selected from the group consisting of LiClO 4 , LiBF 4 , LiAsF 6 , LiCF 3 So 3 , and LiN(CF 3 So 2 ) 2 dissolved in at least one polymer host selected from the group consisting of poly (ethylene oxide), poly(propylene oxide) poly(dioxolane) and poly (methylmethacrylate).
  • Electropolymerized films on the order of one micron in thickness can be prepared to serve as the cathode material, that, when doped with anions on charging, are electronically conductive. Upon discharge, anions return to the electrolyte.
  • Suitable solid polymer cathodes that can be used in the invention include poly(3-methylthirophene) poly(alkyl-thiophene) poly(aniline) poly(acetylene), or mixtures thereof.
  • the invention provides a solid state lithium electrochemical system that utilizes thin, solid polymer films as electrolyte and cathode, and that includes an anode of either metallic lithium or a lithium intercalating material.
  • lithium intercalating materials include lithium alloy, LiC 6 , lithiated graphite, and lithiated petroleum coke.
  • An all-solid state lithium electrochemical cell is made with an ionically conducting SPE and an electronically conductive polymer cathode.
  • the SPE is comprised of lithium salts (LiCF 3 SO 3 , LiN(CF 3 SO 2 ) 2 ) dissolved in poly(ethylene oxide) (PEO).
  • the cathode is poly(3-methylthiophene) (PMT).
  • the polymer cathode accepts anions common to the SPE on charge, and releases anions into the SPE on discharge.
  • lithium ions from the SPE are plated as metallic lithium during charge, and released to the SPE on discharge as seen in the following equation: ##STR1##
  • Electrochemical polymerization of poly(3-methylthiophene) (PMT) films is accomplished in a 125 ml European flask using a 1 cm 2 platinum flag counter electrode, a saturated sodium calomel reference electrode, and a platinum rod working electrode.
  • One end of the working electrode is polished to a mirror finish with an alumina/water paste and sheathed in heat shrinkable Teflon, exposing a 0.071 cm 2 surface area.
  • PMT-covered electrodes are fitted with a small lithium metal reference electrode, then dipped into the polymer solution four or five times. Between each dip, films are allowed to stand to permit the CH 3 CN to evaporate, leaving a solid polymer electrolyte covering the PMT and reference electrodes. Finished electrodes are dried overnight under active vacuum at 50° C.
  • Laboratory cells are constructed by pressing the electrodes against metallic lithium (anodes) and maintaining slight pressure to ensure mechanical contact. Cell cycling is performed galvanostatically with an EG&G PAR Models 173 potentiostat/galvanostat controlled by a HP86B computer.
  • the electrochemical cell or system is:
  • PMT is polymerized with BF 4 as the dopant anion.
  • the cell is discharged at 5 ⁇ A cm -2 to a 2.0 V cutoff, and charged at 2.5 ⁇ A to a 3.8 V cutoff for 170 cycles at a temperature between 19° C. and 22° C. Good retention of capacity is observed and mean cycling efficiency is 98.4%.
  • Initial load potential is above 3.6 V with voltage gradually decreasing until near the end of discharge when voltage drags abruptly from about 3.0 V to the 2.0 V cutoff. There is an increase in capacity over the first few cycles that is explained by an increase in the level of polymer doping as the PMT becomes better able to accommodate anions.
  • This electrochemical system or cell is:
  • the PMT dopant anion (CF 3 SO 3 - ) introduced during electropolymerization is common to anions present in the electrolyte.
  • Discharge (5 ⁇ A cm -2 to 2.0 V) and charge (3.5 ⁇ A cm 2 to 3.8 V) capacity increases over the first few cycles from 2 mA h g -1 to 3.5 mA h g -1 until cycle 19, where capacity drops to 1.2 mA h g -1 . Thereafter, capacity is very consistent, fading to slightly above 1.0 mA h g -1 by cycle 87.
  • the electrochemical cell or system is:
  • the imide anion (N(CF 3 SO 2 ) 2 - ) initially doped into the PMT is also common to the electrolyte. Discharge and charge are both at a rate of 5 ⁇ A cm -2 between voltage cutoffs of 2.0 V and 3.8 V respectively. Capacity increases over the first few cycles to 12.9 mA h g -1 . At cycle 25, capacity falls to 6.6 mA h g -1 then recovers slightly to remain between 7.5 to 8.5 mA h g -1 through cycle 72.

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

Abstract

A lithium electrochemical cell is provided that provides many cycles with loss in capacity. The cell contains an ion conducting solid polymer electrolyte and an electronically conductive, anion-intercalating polymer cathode.

Description

GOVERNMENT INTEREST
The invention described herein may be manufactured, used, and licensed by or for the Government for governmental purposes without the payment to me of any royalty thereon.
FIELD OF INVENTION
The invention relates in general to lithium electrochemical cells and in particular to solid state electrochemical lithium/polymer cells that provide many cycles without a loss in capacity.
BACKGROUND OF THE INVENTION
Two major areas of consideration in the development of lithium electrochemical cells are to find a liquid electrolyte that does not react with metallic lithium and to identify a lithium anion intercalating cathode as for example Lix CoO2, Lix TiS2, and Lix Mn2 O4 that provides many cycles without loss in capacity. The absence of a liquid component would reduce or eliminate corrosion of the metallic lithium anode, as well as harmful chemical reactions at the cathode.
SUMMARY OF THE INVENTION
The general object of this invention is to provide an improved lithium electrochemical cell. A more particular object of the invention is to provide such a cell that does not contain a liquid component that can cause corrosion of the metallic lithium anode as well as harmful chemical reactions at the cathode. A still further object of the invention is to provide such a lithium electrochemical cell that allows for high cycle life and good capacity retention. Another object of the invention is to provide such a lithium electrochemical cell that can be used as either a primary cell or a rechargeable cell.
It has now been found that the aforementioned objects can be attained by making a solid state lithium electrochemical cell that contains an ion conducting solid polymer electrolyte and an electronically conductive, anion intercalating polymer cathode.
Absence of a liquid component reduces or eliminates corrosion of the metallic lithium anode, as well as harmful chemical reactions at the cathode. At the cathode, anions are intercalated rather than cations, with anion-doped polymer being electrically conductive, and undoped polymer being electrically resistive. The polymer cathode is somewhat flexible, allowing anion doping and undoping to occur without structured damage, allowing for high cycle life and good capacity retention.
The use of the solid state lithium electrochemical cells as rechargeable cells allows for the development of thin film rechargeable mono and bipolar lithium cells. The novel features of the cell include a system that is completely solid state. Moreover, polymers are employed as both cathode and electrolyte. Then, too, anions (instead of lithium cations) are shuttled in and out of the cathode. The polymeric electrolyte and cathode components total only a few microns in thickness. This allows for the manufacture of a very thin, multicell, high voltage battery.
Because the system is solid state, any desired geometric form is possible, and battery packages can be sealed in metallized plastic films. This reduces packaging weight considerably compared to the heavy-walled metal cans normally used for cells containing liquid electrolyte.
A solid electrolyte according to the invention includes a polymer host containing dissolved lithium salt, allowing the movement of Li+ and X- ions between the electrodes. There are many advantages associated with the use of ionically conducting polymers as for example (poly (ethylene oxide)) such as high speed processing of thin, light weight bipolar cells. Solid polymer electrolyte (SPE) films can act both as a mechanical separator between the anode and cathode, and as a binder/adhesive to insure contact between electrodes. Elasticity allows the SPE to conform to electrode volume changes during cycling. Further, safety is enhanced in that there is no liquid electrolyte to leak from cells. The SPE that can be used in the invention include at least one lithium salt selected from the group consisting of LiClO4, LiBF4, LiAsF6, LiCF3 So3, and LiN(CF3 So2)2 dissolved in at least one polymer host selected from the group consisting of poly (ethylene oxide), poly(propylene oxide) poly(dioxolane) and poly (methylmethacrylate).
Electropolymerized films on the order of one micron in thickness can be prepared to serve as the cathode material, that, when doped with anions on charging, are electronically conductive. Upon discharge, anions return to the electrolyte. Suitable solid polymer cathodes that can be used in the invention include poly(3-methylthirophene) poly(alkyl-thiophene) poly(aniline) poly(acetylene), or mixtures thereof.
The invention provides a solid state lithium electrochemical system that utilizes thin, solid polymer films as electrolyte and cathode, and that includes an anode of either metallic lithium or a lithium intercalating material. Such lithium intercalating materials include lithium alloy, LiC6, lithiated graphite, and lithiated petroleum coke.
An all-solid state lithium electrochemical cell is made with an ionically conducting SPE and an electronically conductive polymer cathode. The SPE is comprised of lithium salts (LiCF3 SO3, LiN(CF3 SO2)2) dissolved in poly(ethylene oxide) (PEO). The cathode is poly(3-methylthiophene) (PMT). In this cell, the polymer cathode accepts anions common to the SPE on charge, and releases anions into the SPE on discharge. Likewise, lithium ions from the SPE are plated as metallic lithium during charge, and released to the SPE on discharge as seen in the following equation: ##STR1##
Since anions and cations are simply being shuttled between electrodes, no new products are formed during charge or discharge, so no chemical reactions detrimental to cycle life occur. Therefore, exceptional cycle life and capacity are seen.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Electrochemical polymerization of poly(3-methylthiophene) (PMT) films is accomplished in a 125 ml European flask using a 1 cm2 platinum flag counter electrode, a saturated sodium calomel reference electrode, and a platinum rod working electrode. One end of the working electrode is polished to a mirror finish with an alumina/water paste and sheathed in heat shrinkable Teflon, exposing a 0.071 cm2 surface area. The cell is flooded with a solution containing 0.1M 3-methylthiophene monomer dissolved in acetonitrile that also contains a 0.1M concentration of either tetrabutylammonium tetrafluoroborate, LiCF3 SO3, or LiN[(CF3 SO2)]2. Ultra high purity argon is bubbled through the electrolyte to remove any oxygen. The PMT films, 1.4 microns thick, are polymerized at 10 mA cm-2 by passing a charge of 0.25 C cm-2 five (1.25 C cm-2 total), with five minute periods at open circuit between depositions. The PMT- covered electrode is rinsed in acetonitrile and dried under vacuum at 50° C. Polymerized films contain anions corresponding to the salt used: BF4 -, CF3 SO3 -, N(CF3 SO2)2 -.
PEO(MW=4×106), LiCF3 SO3, and LiN(CF3 SO2)2 in a molar ratio of 20:1:1 are dissolved in acetonitrile that has been distilled while bubbling dry argon to form a viscous solution. PMT-covered electrodes are fitted with a small lithium metal reference electrode, then dipped into the polymer solution four or five times. Between each dip, films are allowed to stand to permit the CH3 CN to evaporate, leaving a solid polymer electrolyte covering the PMT and reference electrodes. Finished electrodes are dried overnight under active vacuum at 50° C. Laboratory cells are constructed by pressing the electrodes against metallic lithium (anodes) and maintaining slight pressure to ensure mechanical contact. Cell cycling is performed galvanostatically with an EG&G PAR Models 173 potentiostat/galvanostat controlled by a HP86B computer.
EXAMPLE 1
The electrochemical cell or system is:
Li/(PEO).sub.20 (LiCF.sub.3 SO.sub.3).sub.1, (LiN[CF.sub.3 S).sub.2 ].sub.2).sub.1 /PMT-BF.sub.4.sup.-
In this cell, PMT is polymerized with BF4 as the dopant anion. The cell is discharged at 5 μA cm-2 to a 2.0 V cutoff, and charged at 2.5 μA to a 3.8 V cutoff for 170 cycles at a temperature between 19° C. and 22° C. Good retention of capacity is observed and mean cycling efficiency is 98.4%. Initial load potential is above 3.6 V with voltage gradually decreasing until near the end of discharge when voltage drags abruptly from about 3.0 V to the 2.0 V cutoff. There is an increase in capacity over the first few cycles that is explained by an increase in the level of polymer doping as the PMT becomes better able to accommodate anions.
EXAMPLE 2
This electrochemical system or cell is:
Li/(PEO).sub.20 (LiCF.sub.3 SO.sub.3).sub.1 (LiN[CF.sub.3 SO.sub.2 ].sub.2).sub.1 /PMT-CF.sub.3 SO.sub.3.sup.-
In this cell, the PMT dopant anion (CF3 SO3 -) introduced during electropolymerization is common to anions present in the electrolyte. Discharge (5 μA cm-2 to 2.0 V) and charge (3.5 μA cm2 to 3.8 V) capacity increases over the first few cycles from 2 mA h g-1 to 3.5 mA h g-1 until cycle 19, where capacity drops to 1.2 mA h g-1. Thereafter, capacity is very consistent, fading to slightly above 1.0 mA h g-1 by cycle 87.
EXAMPLE 3
The electrochemical cell or system is:
Li/(PEO).sub.20 (LiCF.sub.3 SO.sub.3).sub.1 (LiN[CF.sub.3 SO.sub.2 ].sub.2).sub.1 /PMT-N(CF.sub.3 SO.sub.2).sub.2.sup.-
In this instance, the imide anion (N(CF3 SO2)2 -) initially doped into the PMT is also common to the electrolyte. Discharge and charge are both at a rate of 5 μA cm-2 between voltage cutoffs of 2.0 V and 3.8 V respectively. Capacity increases over the first few cycles to 12.9 mA h g-1. At cycle 25, capacity falls to 6.6 mA h g-1 then recovers slightly to remain between 7.5 to 8.5 mA h g-1 through cycle 72.
I wish it to be understood that I do not desire to be limited to the exact details of construction shown and described for obvious modifications will occur to a person skilled in the art.

Claims (4)

What is claimed is:
1. A solid state electrochemical cell including metallic lithium as an anode, (PEO)20 (LiCF3 SO3)1 (LiN[CF3 SO2 ]) as a solid polymer electrolyte and and poly (3-methylthiophene as a solid polymer cathode.
2. A solid state electrochemical cell including metallic lithium as an anode, (PEO)20 (LiCF3 SO3)1 (LiN[CF3 SO2 ]2)1 as a solid polymer electrolyte and poly 3-methylthiophene-BF4 as a solid polymer cathode.
3. A solid state electrochemical cell including metallic lithium, as an anode, PEO)20 (LiCF3 SO3)1 (LiN[CF3 SO2 ]2)1 as a solid polymer electrolyte and poly(3-methylthiophene-CF3 SO3 as solid polymer cathode.
4. A solid state electrochemical cell including metallic lithium as an anode, (PEO)20 (LICF3 SO3)1 (LiN[CF3 SO2 ]2)1 as a solid polymer electrolyte, and poly(3-methylthiophene)-N(CF3 SO2)2 as a solid polymer cathode.
US08/153,948 1993-11-01 1993-11-01 Solid state electrochemical lithium/polymer cell Abandoned USH1462H (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5827602A (en) * 1995-06-30 1998-10-27 Covalent Associates Incorporated Hydrophobic ionic liquids
US5985487A (en) * 1995-04-12 1999-11-16 Valence Technology, Inc. Curable alkane multifunctional acrylates based solid electrolytes and electrolytic cells produced therefrom
US6699621B2 (en) * 1996-10-30 2004-03-02 Johns Hopkins University Method for electrochemical conditioning polymeric electrodes
EP0947014A4 (en) * 1996-10-30 2005-12-28 Univ Johns Hopkins ELECTROCHEMICAL ACCUMULATOR CELL COMPRISING AT LEAST ONE ELECTRODE BASED ON A FLUOROPHENYL THIOPHENE POLYMER

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4543306A (en) * 1982-06-01 1985-09-24 Thomson-Csf Electrochemical device which can be used for energy storage
US4939050A (en) * 1987-11-12 1990-07-03 Bridgestone Corporation Electric cells
US5225296A (en) * 1989-11-21 1993-07-06 Ricoh Company, Ltd. Electrode and method of producing the same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4543306A (en) * 1982-06-01 1985-09-24 Thomson-Csf Electrochemical device which can be used for energy storage
US4939050A (en) * 1987-11-12 1990-07-03 Bridgestone Corporation Electric cells
US5225296A (en) * 1989-11-21 1993-07-06 Ricoh Company, Ltd. Electrode and method of producing the same

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5985487A (en) * 1995-04-12 1999-11-16 Valence Technology, Inc. Curable alkane multifunctional acrylates based solid electrolytes and electrolytic cells produced therefrom
US5827602A (en) * 1995-06-30 1998-10-27 Covalent Associates Incorporated Hydrophobic ionic liquids
US6699621B2 (en) * 1996-10-30 2004-03-02 Johns Hopkins University Method for electrochemical conditioning polymeric electrodes
EP0947014A4 (en) * 1996-10-30 2005-12-28 Univ Johns Hopkins ELECTROCHEMICAL ACCUMULATOR CELL COMPRISING AT LEAST ONE ELECTRODE BASED ON A FLUOROPHENYL THIOPHENE POLYMER

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