USH1335H - High temperature molten salt thermal cell - Google Patents

High temperature molten salt thermal cell Download PDF

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Publication number
USH1335H
USH1335H US08/014,606 US1460693A USH1335H US H1335 H USH1335 H US H1335H US 1460693 A US1460693 A US 1460693A US H1335 H USH1335 H US H1335H
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United States
Prior art keywords
lithium
high temperature
molten salt
thermal cell
temperature molten
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Abandoned
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US08/014,606
Inventor
Edward J. Plichta
Wishvender K. Behl
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United States Department of the Army
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United States Department of the Army
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Priority to US08/014,606 priority Critical patent/USH1335H/en
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Publication of USH1335H publication Critical patent/USH1335H/en
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    • 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
    • H01M4/581Chalcogenides or intercalation compounds thereof
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00Primary cells; Manufacture thereof
    • H01M6/30Deferred-action cells
    • H01M6/36Deferred-action cells containing electrolyte and made operational by physical means, e.g. thermal cells

Definitions

  • the invention relates in general to high temperature molten salt thermal cells and in particular to such cells where the active cathode material is thermally stable at high temperatures an also provides high specific energy densities and specific power densities.
  • High temperature molten salt thermal cells have been required for applications in fuses, projectile rockets, bombs, missiles, decoys, jammers, and torpedos.
  • the lithium alloy/metal sulfide cells have shown considerable promise for these applications.
  • the general object of this invention is to provide a high temperature molten salt thermal cell where the active cathode material is thermally stable at high temperatures and also provides high specific energy densities and specific power densities.
  • the active cathodic materials include at least one of the binary sulfides of chromium metal such as CrS, Cr 3 S 4 , or Cr 2 S 3 .
  • Use of these cathodic materials in an electrochemical cell including a Li-A1 alloy anode and a molten LiCl-LiF-LiBr electrolyte has been demonstrated to deliver specific energy densities of about 219 Wh/kg at a current density of 100 mA/cm 2 at an operating temperature of 490° C.
  • the electrochemical cell described herein includes a lithium-aluminum alloy of 48 atomic percent lithium as the anode, an all lithium halide mixture of 47 mole percent lithium fluoride, 31 mole percent lithium chloride and 22 mole percent lithium bromide with a melting point of 445° C. as the electrolyte, and chromium sesquisulfide (Cr 2 S 3 )as the cathode active material.
  • the discharge reactions of the cell may be represented by the following reactions:
  • the electrochemical cell includes a three pellet stack of anode, electrolyte and cathode held together by a spring loaded cell design.
  • FIG. 1 shows a typical discharge curve of the cell at a current density of 100mA/cm 2 at an operating temperature of 490° C.
  • the cell delivers an energy density of 219 Wh/kg and a power density of 0.47 kW/kg at a current density of 100 mA/cm 2 .
  • the molten alkali metal halide electrolyte of the high temperature molten salt thermal cell may also be at least one compound of the group LiAlCl 4 , NaAlCl 4 , LiCl, LiF, LiBr, NaCl, NaF, NaBr, KCl, KF, and KBr.
  • anode of the high temperature molten salt electrochemical cell one might use at least one member of the group consisting of Li, LiAl, Na, K, Ca, Mg or any alkali metal or group IIA element, or alloy or composite mixture of at least two members of the group.
  • the separator material of the high temperature molten salt thermal cell may be electrically insulative such as MgO, Y 2 O 3 , ZrO 2 or ionically conductive material such as Beta alumina.
  • the separation between the anode and the cathode may be provided by a 65 weight percent molten salt electrolyte including any alkali or alkaline earth chloride, fluoride or bromide with 35 weight percent of a separator material as referred to previously.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Primary Cells (AREA)
  • Secondary Cells (AREA)

Abstract

A high temperature molten salt thermal cell is provided including an alkalietal containing anode, a molten lithium halide electrolyte and at least one binary sulfide of chromium as the 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 us of any royalties thereon.
FIELD OF INVENTION
The invention relates in general to high temperature molten salt thermal cells and in particular to such cells where the active cathode material is thermally stable at high temperatures an also provides high specific energy densities and specific power densities.
BACKGROUND OF THE INVENTION
High temperature molten salt thermal cells have been required for applications in fuses, projectile rockets, bombs, missiles, decoys, jammers, and torpedos. Amongst the many molten salt thermal cell systems that have been studied over the past many years, the lithium alloy/metal sulfide cells have shown considerable promise for these applications. In the past, these cells have used a lithium alloy (Li-A1) as the anode, an electrolyte including a lithium halide-alkali halide mixture (LiCl-KCl) eutectic and a cathode having as the cathode active material a binary metal sulfide of the general formula YS or YS2 where Y=Fe, Co or Ni. Though the use of these cathode materials has been generally satisfactory, it would be desirable to obtain cathode material that can deliver even higher energy densities at high temperatures.
SUMMARY OF THE INVENTION
The general object of this invention is to provide a high temperature molten salt thermal cell where the active cathode material is thermally stable at high temperatures and also provides high specific energy densities and specific power densities.
It has now been found that the aforementioned objective can be attained by providing a molten salt electrochemical thermal cell where the active cathodic materials include at least one of the binary sulfides of chromium metal such as CrS, Cr3 S4, or Cr2 S3. Use of these cathodic materials in an electrochemical cell including a Li-A1 alloy anode and a molten LiCl-LiF-LiBr electrolyte has been demonstrated to deliver specific energy densities of about 219 Wh/kg at a current density of 100 mA/cm2 at an operating temperature of 490° C.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The electrochemical cell described herein includes a lithium-aluminum alloy of 48 atomic percent lithium as the anode, an all lithium halide mixture of 47 mole percent lithium fluoride, 31 mole percent lithium chloride and 22 mole percent lithium bromide with a melting point of 445° C. as the electrolyte, and chromium sesquisulfide (Cr2 S3)as the cathode active material. The discharge reactions of the cell may be represented by the following reactions:
3Cr.sub.2 S.sub.3 +2LiA1→2Cr.sub.3 S.sub.4 +Li.sub.2 S+2A1
2Cr.sub.3 S.sub.4 +4LiA1→6CrS+2Li.sub.2 S+4A1
6CrS+12LiA1→6Li.sub.2 S+12A1+6Cr
The electrochemical cell includes a three pellet stack of anode, electrolyte and cathode held together by a spring loaded cell design.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 shows a typical discharge curve of the cell at a current density of 100mA/cm2 at an operating temperature of 490° C.
DESCRIPTION OF THE DRAWING
Referring to FIG. 1, the cell delivers an energy density of 219 Wh/kg and a power density of 0.47 kW/kg at a current density of 100 mA/cm2.
In lieu of the all lithium halide electrolyte mixture of lithium fluoride, lithium chloride and lithium bromide, a eutectic mixture of 59 mole percent lithium chloride and 41 mole percent potassium chloride maybe used as the electrolyte. The molten alkali metal halide electrolyte of the high temperature molten salt thermal cell may also be at least one compound of the group LiAlCl4, NaAlCl4, LiCl, LiF, LiBr, NaCl, NaF, NaBr, KCl, KF, and KBr.
As the anode of the high temperature molten salt electrochemical cell, one might use at least one member of the group consisting of Li, LiAl, Na, K, Ca, Mg or any alkali metal or group IIA element, or alloy or composite mixture of at least two members of the group.
The separator material of the high temperature molten salt thermal cell may be electrically insulative such as MgO, Y2 O3, ZrO2 or ionically conductive material such as Beta alumina. The separation between the anode and the cathode may be provided by a 65 weight percent molten salt electrolyte including any alkali or alkaline earth chloride, fluoride or bromide with 35 weight percent of a separator material as referred to previously.
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 (7)

What is claimed is:
1. A high temperature molten salt thermal cell including an alkali metal containing anode, a molten alkali metal halide electrolyte and at least one binary sulfide of chromium as the cathode.
2. A high temperature molten salt thermal cell according to claim 1 wherein the alkali metal containing anode is at least one member of the group consisting of lithium, lithium-aluminum alloys, lithium-silicon alloys, lithium-boron alloys, sodium, sodium-alloys, potassium, calcium, and magnesium.
3. A high temperature molten salt thermal cell according to claim 1, wherein the binary sulfide of chromium is at least one member of the group consisting of Cr2 S3, Cr3 S4 and CrS.
4. A high temperature molten salt thermal cell according to claim 1 wherein the molten alkali halide electrolyte is at least one member of the group consisting of LiAlCl4, NaAlCl4, LiCl, LiF, LiBr, NaCl, NaF, NaBr, KCl, KF, and KBr.
5. A high temperature molten salt thermal cell according to claim 3 wherein the molten alkali metal halide electrolyte is a eutectic mixture of about 47 mole percent lithium bromide, about 31 mole percent lithium chloride, and about 22 mole percent lithium fluoride.
6. A high temperature molten salt thermal cell according to claim 3 wherein the molten alkali metal halide electrolyte is a eutectic mixture of about 59 mole percent lithium chloride and about 41 percent potassium chloride.
7. A high temperature molten salt thermal cell including a lithium aluminum alloy of about 48 atomic percent of lithium as the anode, a lithium halide eutectic mixture of about 31 mole percent lithium chloride, about 47 mole percent lithium bromide, and about 22 mole percent lithium fluoride as the electrolyte, and chromium sesquisulfide as the cathode.
US08/014,606 1993-02-08 1993-02-08 High temperature molten salt thermal cell Abandoned USH1335H (en)

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USH1335H true USH1335H (en) 1994-07-05

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100221616A1 (en) * 2008-11-07 2010-09-02 Eaglepicher Technologies, Llc Non-aqueous cell having amorphous or semi-crystalline copper manganese oxide cathode material
WO2010117954A1 (en) * 2009-04-06 2010-10-14 Eaglepicher Technologies, Llc Thermal battery electrolyte compositions, electrode-electrolyte composites, and batteries including the same
US20100310907A1 (en) * 2009-03-05 2010-12-09 Eaglepicher Technologies, Llc End of life indication system and method for non-aqueous cell having amorphous or semi-crystalline copper manganese oxide cathod material
US20100310908A1 (en) * 2009-03-18 2010-12-09 Eaglepicher Technologies, Llc Non-aqueous electrochemical cell having a mixture of at least three cathode materials therein
US20100308253A1 (en) * 2009-04-06 2010-12-09 Eaglepicher Technologies, Llc Thermal battery cathode materials and batteries including same
US8652674B2 (en) 2010-06-24 2014-02-18 Eaglepicher Technologies, Llc Thermal battery cathode materials containing nickel disulfide and batteries including same
CN109378460A (en) * 2018-10-24 2019-02-22 上海空间电源研究所 A kind of 5Ah grades of single cell of thermo battery
CN110534697A (en) * 2019-09-11 2019-12-03 中国工程物理研究院电子工程研究所 A kind of single cell of thermo battery and preparation method thereof
CN114843704A (en) * 2022-04-20 2022-08-02 天津大学 A manganese-containing fluoride thermal battery

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3898096A (en) 1973-06-11 1975-08-05 Rockwell International Corp Lithium-molten salt cell with transition metal chalcogenide positive electrode

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3898096A (en) 1973-06-11 1975-08-05 Rockwell International Corp Lithium-molten salt cell with transition metal chalcogenide positive electrode

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8669007B2 (en) 2008-11-07 2014-03-11 Eaglepicher Technologies, LLC. Non-aqueous cell having amorphous or semi-crystalline copper manganese oxide cathode material
US20100221616A1 (en) * 2008-11-07 2010-09-02 Eaglepicher Technologies, Llc Non-aqueous cell having amorphous or semi-crystalline copper manganese oxide cathode material
US20100310907A1 (en) * 2009-03-05 2010-12-09 Eaglepicher Technologies, Llc End of life indication system and method for non-aqueous cell having amorphous or semi-crystalline copper manganese oxide cathod material
US8663825B2 (en) 2009-03-05 2014-03-04 Eaglepicher Technologies, Llc End of life indication system and method for non-aqueous cell having amorphous or semi-crystalline copper manganese oxide cathode material
US8623553B2 (en) 2009-03-18 2014-01-07 Eaglepicher Technologies, Llc Non-aqueous electrochemical cell having a mixture of at least three cathode materials therein
US20100310908A1 (en) * 2009-03-18 2010-12-09 Eaglepicher Technologies, Llc Non-aqueous electrochemical cell having a mixture of at least three cathode materials therein
US20100308253A1 (en) * 2009-04-06 2010-12-09 Eaglepicher Technologies, Llc Thermal battery cathode materials and batteries including same
US8440342B2 (en) 2009-04-06 2013-05-14 Eaglepicher Technologies, Llc Thermal battery cathode materials and batteries including same
US8394520B2 (en) 2009-04-06 2013-03-12 Eaglepicher Technologies, Llc Thermal battery electrolyte materials, electrode-electrolyte composites, and batteries including same
US20100310917A1 (en) * 2009-04-06 2010-12-09 Eaglepicher Technologies, Llc Thermal battery electrolyte materials, electrode-electrolyte composites, and batteries including same
WO2010117954A1 (en) * 2009-04-06 2010-10-14 Eaglepicher Technologies, Llc Thermal battery electrolyte compositions, electrode-electrolyte composites, and batteries including the same
US8652674B2 (en) 2010-06-24 2014-02-18 Eaglepicher Technologies, Llc Thermal battery cathode materials containing nickel disulfide and batteries including same
CN109378460A (en) * 2018-10-24 2019-02-22 上海空间电源研究所 A kind of 5Ah grades of single cell of thermo battery
CN109378460B (en) * 2018-10-24 2021-09-10 上海空间电源研究所 5 Ah-level thermal battery single battery
CN110534697A (en) * 2019-09-11 2019-12-03 中国工程物理研究院电子工程研究所 A kind of single cell of thermo battery and preparation method thereof
CN110534697B (en) * 2019-09-11 2022-03-01 中国工程物理研究院电子工程研究所 Thermal battery single battery and preparation method thereof
CN114843704A (en) * 2022-04-20 2022-08-02 天津大学 A manganese-containing fluoride thermal battery

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