USH1545H - Oxyhalide electrochemical cell including an alkali metal intercalated carbon as the anode - Google Patents

Oxyhalide electrochemical cell including an alkali metal intercalated carbon as the anode Download PDF

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Publication number
USH1545H
USH1545H US08/340,925 US34092594A USH1545H US H1545 H USH1545 H US H1545H US 34092594 A US34092594 A US 34092594A US H1545 H USH1545 H US H1545H
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Prior art keywords
oxyhalide
electrochemical cell
alkali metal
anode
carbon
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US08/340,925
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Edward J. Plichta
Wishvender K. Behl
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US Department of Army
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US Department of Army
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00Primary cells; Manufacture thereof
    • H01M6/14Cells with non-aqueous electrolyte
    • H01M6/16Cells with non-aqueous electrolyte with organic electrolyte
    • H01M6/162Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
    • H01M6/164Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by the solvent
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/056Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564Accumulators 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
    • H01M10/0566Liquid materials
    • H01M10/0568Liquid materials characterised by the solutes
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/056Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564Accumulators 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
    • H01M10/0566Liquid materials
    • H01M10/0569Liquid materials characterised by the solvents
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00Primary cells; Manufacture thereof
    • H01M6/14Cells with non-aqueous electrolyte
    • H01M6/16Cells with non-aqueous electrolyte with organic electrolyte
    • H01M6/162Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
    • H01M6/166Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by the solute
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Definitions

  • the invention relates in general to oxyhalide electrochemical cells, and in particular, to oxyhalide electrochemical cell that include an alkali metal intercalated carbon as the anode.
  • lithium/oxyhalide chemistries offer high energy densities and are capable of high current densities.
  • these cells consist of a lithium or calcium metal anode and a high surface area carbon cathode, that acts as the depolarizer for the reduction of the oxyhalide solvent in the electrolyte.
  • these cells offer excellent electrochemical performance, they suffer from inherent safety problems brought about by the use of the reactive lithium metal anodes.
  • Safety studies on the cell components in lithium/oxyhalide cells associated the safety problems with runaway type reactions with the lithium metal anode that resulted in cell explosions under abuse test conditions.
  • the general object of this invention is to provide an oxyhalide electrochemical cell in which the aforementioned difficulties are overcome.
  • a more particular object of the invention is to provide such an oxyhalide electrochemical cell that does not require the use of alkali metals as the anode, and that provides safe operation and excellent performance with no cell voltage delay.
  • the cell also uses a high surface area carbon black as the cathode and a solution of an alkali metal salt in an oxyhalide solvent as the electrolyte.
  • high temperature molten salt cells can be made that use an alkali metal petroleum coke as for example, a lithiated petroleum coke as the anode that provides significant cell cycling at cell voltages similar to those obtained using more costly lithium metal alloy anodes.
  • "Petroleum coke” as the term is used herein refers to a petroleum based carbon black.
  • a 1 cm ⁇ 1 cm graphite electrode is made using a 90 weight percent graphite and 10 weight percent Teflon mixture that is roll pressed onto an expanded nickel grid followed by vacuum drying at 100° C. for 48 hours.
  • the graphite electrode is intercalated with lithium via electrochemical reduction versus a lithium metal electrode in an electrolyte consisting of a one molar concentration of LiAsF 6 in dimethyl carbonate.
  • the graphite electrode is intercalated with lithium at 1 mA current (0.17 mA/cm 2 ) to a cell voltage versus lithium of 0.02 volts.
  • the degree of lithiation is 90% that corresponds to the phase LiC 6 and a lithium capacity of 23.1 mAh or 0.33 Ah/g.
  • the intercalated graphite electrode is then rinsed with pure dimethyl carbonate to remove the LiAsF 6 salt and dried under vacuum to remove the organic solvent.
  • the lithium intercalation of the graphite can also be done by chemically reacting the graphite in molten lithium metal.
  • a control cell using a similar cathode versus lithium metal in an electrolyte of 1.5 M LiAlCl 4 in thionyl chloride determines the cathode capacity to be 41.3 mAh or 2.3 Ah/g for the 5 mA rate (5 mA/cm 2 ).
  • the oxyhalide electrolyte is prepared as 1.5 molar LiAlCl 4 in thionyl chloride.
  • the lithiated graphite anode and shawinigan black carbon cathode are sandwiched between a single layer of glass fiber separator, that acts as a wick for the electrolyte. The cell is held in compression through the use of two glass slides and Teflon clips.
  • the assembled cell is contained in a Pyrex glass pressure vessel affixed with Viton O-ring seals and electrical feed throughs.
  • the cell is filled with the oxyhalide electrolyte and operated in an electrolyte starved condition.
  • the intercalated graphite electrode handling and preparation as well as the oxyhalide cell construction is done in an argon filled dry box that is maintained at ⁇ 0.5 ppm water.
  • the electrolyte is prepared, and the cell filled in a dry room controlled to ⁇ 1% relative humidity.
  • FIG. 1 shows the discharge obtained for the LiC 6 /1.5 M LiAlCl 4 in thionyl chloride/(shawinigan black) cell just described.
  • the cell open circuit voltage is 3.52 volts.
  • Galvanostatic discharge at (5mA/cm 2 ) to a cell potential of 1 volt results in 6.5 mAh cell capacity at an average cell potential of 2.95 volts.
  • the cell results are not optimized due to the electrolyte starved conditions used. No voltage delay is seen for the cell during discharge from the open circuit potential at a temperature of 25° C. It is expected that even after long term storage, no cell voltage delay will be observed since lithiated carbon does not form the passivating films typical for lithium metal.
  • cathodes can be used in the oxyhalide cells in lieu of shawinigan black such as those carbons known as high surface area carbon blacks, graphite, petroleum cokes, charcoals, soots, and fullerenes. Additional additives to the cathode can also be used to enhance the catalytic reduction of the oxyhalide.
  • oxyhalides can be used in lieu of thionyl chloride such as SO 2 Cl 2 , POCl 3 , CSCl 2 , CH 3 CClO, Si 2 OCl 6 , P 2 O 3 Cl 4 , and S 2 O 5 Cl 2 .
  • LiAlCl 4 LiBCl 4 , Li 2 B 10 Cl 10 , and Li 2 B 12 Cl 12 .

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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)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Primary Cells (AREA)

Abstract

An oxyhalide electrochemical cell is provided including an alkali metal ircalated carbon as the anode, a high surface area carbon black as the cathode, and a solution of an alkali metal salt in an oxyhalide solvent as the electrolyte.

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 us of any royalties thereon.
FIELD OF INVENTION
The invention relates in general to oxyhalide electrochemical cells, and in particular, to oxyhalide electrochemical cell that include an alkali metal intercalated carbon as the anode.
BACKGROUND OF THE INVENTION
Alkali metal/oxyhalide chemistries and in particular, lithium/oxyhalide chemistries offer high energy densities and are capable of high current densities. Typically, these cells consist of a lithium or calcium metal anode and a high surface area carbon cathode, that acts as the depolarizer for the reduction of the oxyhalide solvent in the electrolyte. However, although these cells offer excellent electrochemical performance, they suffer from inherent safety problems brought about by the use of the reactive lithium metal anodes. Safety studies on the cell components in lithium/oxyhalide cells associated the safety problems with runaway type reactions with the lithium metal anode that resulted in cell explosions under abuse test conditions. In addition to the safety concerns, the lithium metal anodes suffered from electrochemical passivation after storage, that results in cell voltage delays and reduces performance. Finally, the use of lithium or calcium metals as anodes in these cells makes fresh cells a hazardous waste and therefore expensive to dispose of safely.
SUMMARY OF THE INVENTION
The general object of this invention is to provide an oxyhalide electrochemical cell in which the aforementioned difficulties are overcome. A more particular object of the invention is to provide such an oxyhalide electrochemical cell that does not require the use of alkali metals as the anode, and that provides safe operation and excellent performance with no cell voltage delay.
It has now been found that the aforementioned object can be attained by using an alkali metal intercalated carbon as the anode in the oxyhalide electrochemical cell. The cell also uses a high surface area carbon black as the cathode and a solution of an alkali metal salt in an oxyhalide solvent as the electrolyte.
That is, high temperature molten salt cells can be made that use an alkali metal petroleum coke as for example, a lithiated petroleum coke as the anode that provides significant cell cycling at cell voltages similar to those obtained using more costly lithium metal alloy anodes. "Petroleum coke" as the term is used herein refers to a petroleum based carbon black.
DESCRIPTION OF THE PREFERRED EMBODIMENT
A 1 cm×1 cm graphite electrode is made using a 90 weight percent graphite and 10 weight percent Teflon mixture that is roll pressed onto an expanded nickel grid followed by vacuum drying at 100° C. for 48 hours. The graphite electrode is intercalated with lithium via electrochemical reduction versus a lithium metal electrode in an electrolyte consisting of a one molar concentration of LiAsF6 in dimethyl carbonate. The graphite electrode is intercalated with lithium at 1 mA current (0.17 mA/cm2) to a cell voltage versus lithium of 0.02 volts. The degree of lithiation is 90% that corresponds to the phase LiC6 and a lithium capacity of 23.1 mAh or 0.33 Ah/g. The intercalated graphite electrode is then rinsed with pure dimethyl carbonate to remove the LiAsF6 salt and dried under vacuum to remove the organic solvent. The lithium intercalation of the graphite can also be done by chemically reacting the graphite in molten lithium metal. The 1 cm=1 cm cathode for the oxyhalide cell is fabricated using a 90 wt% high surface area carbon (shawinigan black) and 10 wt% Teflon mixture that is roll pressed onto an expanded nickel grid followed by vacuum drying at 100° C. for 48 hours. A control cell using a similar cathode versus lithium metal in an electrolyte of 1.5 M LiAlCl4 in thionyl chloride determines the cathode capacity to be 41.3 mAh or 2.3 Ah/g for the 5 mA rate (5 mA/cm2). The oxyhalide electrolyte is prepared as 1.5 molar LiAlCl4 in thionyl chloride. The lithiated graphite anode and shawinigan black carbon cathode are sandwiched between a single layer of glass fiber separator, that acts as a wick for the electrolyte. The cell is held in compression through the use of two glass slides and Teflon clips. The assembled cell is contained in a Pyrex glass pressure vessel affixed with Viton O-ring seals and electrical feed throughs. The cell is filled with the oxyhalide electrolyte and operated in an electrolyte starved condition. The intercalated graphite electrode handling and preparation as well as the oxyhalide cell construction is done in an argon filled dry box that is maintained at <0.5 ppm water. The electrolyte is prepared, and the cell filled in a dry room controlled to <1% relative humidity.
DESCRIPTION OF THE DRAWING
FIG. 1 shows the discharge obtained for the LiC6 /1.5 M LiAlCl4 in thionyl chloride/(shawinigan black) cell just described.
Referring to FIG. 1, the cell open circuit voltage is 3.52 volts. Galvanostatic discharge at (5mA/cm2) to a cell potential of 1 volt results in 6.5 mAh cell capacity at an average cell potential of 2.95 volts. The cell results are not optimized due to the electrolyte starved conditions used. No voltage delay is seen for the cell during discharge from the open circuit potential at a temperature of 25° C. It is expected that even after long term storage, no cell voltage delay will be observed since lithiated carbon does not form the passivating films typical for lithium metal.
Other cathodes can be used in the oxyhalide cells in lieu of shawinigan black such as those carbons known as high surface area carbon blacks, graphite, petroleum cokes, charcoals, soots, and fullerenes. Additional additives to the cathode can also be used to enhance the catalytic reduction of the oxyhalide.
Other oxyhalides can be used in lieu of thionyl chloride such as SO2 Cl2, POCl3, CSCl2, CH3 CClO, Si2 OCl6, P2 O3 Cl4, and S2 O5 Cl2.
Other electrolyte salts can also be used in lieu of LiAlCl4 such as LiBCl4, Li2 B10 Cl10, and Li2 B12 Cl12.
The theoretical energy density of the LiC6 /1.5 M LiAlCl4 in thionyl chloride/C (shawinigan black) cell based on the following cell reaction, 4LiC6 +2SOCl2 →S+SO2 +4LiCl+24C, and a cell potential of 3.5 volts is 677 Wh/kg.
We wish it to be understood that we 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 (9)

What is claimed is:
1. An oxyhalide electrochemical cell including an alkali metal intercalated carbon as the anode.
2. An oxyhalide electrochemical cell according to claim 1 wherein the alkali metal is lithium.
3. An oxyhalide electrochemical cell according to claim 1 wherein the alkali metal is calcium.
4. An oxyhalide electrochemical cell according to claim 1 wherein the carbon is a high surface area carbon black.
5. An oxyhalide electrochemical cell according to claim 4 wherein the high surface area carbon black is selected from the group consisting of graphite, petroleum coke, charcoals, soots, and fullerenes.
6. An oxyhalide electrochemical cell according to claim 5 wherein the high surface area carbon black is graphite.
7. An oxyhalide electrochemical cell including an alkali metal intercalated carbon as the anode, a high surface area carbon black as the cathode, and a solution of an alkali metal salt in an oxyhalide solvent as the electrolyte.
8. An oxyhalide electrochemical cell according to claim 7 wherein the alkali metal of the anode is selected from the group consisting of lithium and calcium, the intercalated carbon of the anode is selected from the group of carbons consisting of graphite, petroleum coke, carbon black, charcoals, soots, and fullerenes, wherein the high surface area carbon black of the cathode is selected from the group consisting of graphite, petroleum coke, charcoals, soots, and fullerenes, wherein the alkali metal salt is a lithium salts selected from the group consisting of LiAlCl4, LiBCl4, Li2 B10 Cl10 and Li2 B12 Cl12, and wherein the oxyhalide solvent is an oxychloride solvent selected from the group consisting of SOCl2, SO2 Cl2, POCl3, CSCl2, CH3 CClO, Si2 OCl6, P2 O3 Cl4, and S2 O5 Cl2.
9. An oxyhalide electrochemical cell according to claim 8 wherein the lithium intercalated carbon anode is LiC6, wherein the carbon cathode is shawinigan black, and wherein the electrolyte is a solution of LiAlCl4 in SOCl2.
US08/340,925 1994-11-17 1994-11-17 Oxyhalide electrochemical cell including an alkali metal intercalated carbon as the anode Abandoned USH1545H (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040091783A1 (en) * 2001-05-29 2004-05-13 Cagle Dawson W. Fullerene-based secondary cell electrodes
US20050158626A1 (en) * 2001-05-29 2005-07-21 Wagner Michael J. Fullerene-based secondary cell electrodes
US20180019072A1 (en) * 2016-07-15 2018-01-18 Nanotek Instuments, Inc. Electrochemical Method of Producing Graphene-Based Supercapacitor Electrode from Coke or Coal

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4707423A (en) * 1982-06-10 1987-11-17 Celanese Corporation Electric storage battery and process for the manufacture thereof
US4752540A (en) * 1987-06-05 1988-06-21 Honeywell Inc. Polymeric enclosures for non-aqueous active metal cells
US5028500A (en) * 1989-05-11 1991-07-02 Moli Energy Limited Carbonaceous electrodes for lithium cells
US5352546A (en) * 1993-03-10 1994-10-04 Alliant Techsystems Inc. High rate electrochemical cell

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4707423A (en) * 1982-06-10 1987-11-17 Celanese Corporation Electric storage battery and process for the manufacture thereof
US4752540A (en) * 1987-06-05 1988-06-21 Honeywell Inc. Polymeric enclosures for non-aqueous active metal cells
US5028500A (en) * 1989-05-11 1991-07-02 Moli Energy Limited Carbonaceous electrodes for lithium cells
US5352546A (en) * 1993-03-10 1994-10-04 Alliant Techsystems Inc. High rate electrochemical cell

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040091783A1 (en) * 2001-05-29 2004-05-13 Cagle Dawson W. Fullerene-based secondary cell electrodes
US20050158626A1 (en) * 2001-05-29 2005-07-21 Wagner Michael J. Fullerene-based secondary cell electrodes
US7129003B2 (en) 2001-05-29 2006-10-31 Itt Manufacturing Enterprises, Inc. Fullerene-based secondary cell electrodes
US7531273B2 (en) 2001-05-29 2009-05-12 Itt Manufacturing Enterprises, Inc. Fullerene-based secondary cell electrodes
US20180019072A1 (en) * 2016-07-15 2018-01-18 Nanotek Instuments, Inc. Electrochemical Method of Producing Graphene-Based Supercapacitor Electrode from Coke or Coal

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