CA1116232A - Solid state cell with halogen-chalcogen-metal solid cathode - Google Patents
Solid state cell with halogen-chalcogen-metal solid cathodeInfo
- Publication number
- CA1116232A CA1116232A CA308,563A CA308563A CA1116232A CA 1116232 A CA1116232 A CA 1116232A CA 308563 A CA308563 A CA 308563A CA 1116232 A CA1116232 A CA 1116232A
- Authority
- CA
- Canada
- Prior art keywords
- solid
- solid state
- cell
- cathode
- anode
- 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.)
- Expired
Links
- 239000007787 solid Substances 0.000 title claims abstract description 51
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 5
- 239000002184 metal Substances 0.000 title claims abstract description 5
- 150000001787 chalcogens Chemical group 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 229910052798 chalcogen Inorganic materials 0.000 claims abstract description 9
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 9
- 150000002367 halogens Chemical class 0.000 claims abstract description 8
- 125000004429 atom Chemical group 0.000 claims abstract description 6
- 125000005843 halogen group Chemical group 0.000 claims abstract description 3
- 239000003792 electrolyte Substances 0.000 claims description 11
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical group [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 11
- -1 alkali metal salt Chemical class 0.000 claims description 9
- 239000007784 solid electrolyte Substances 0.000 claims description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 5
- 229910052740 iodine Inorganic materials 0.000 claims description 5
- 239000011630 iodine Substances 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- YPMZHGJQYGMKBQ-UHFFFAOYSA-M [I-].[Bi+]=O Chemical compound [I-].[Bi+]=O YPMZHGJQYGMKBQ-UHFFFAOYSA-M 0.000 claims description 3
- 239000004020 conductor Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 229910052711 selenium Inorganic materials 0.000 claims description 3
- 229910002916 BiTeI Inorganic materials 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910015656 MoOF4 Inorganic materials 0.000 claims description 2
- 229910019201 POBr3 Inorganic materials 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- QLHSJLGUZLTUFP-UHFFFAOYSA-N arsenic oxide monochloride Chemical compound Cl[As]=O QLHSJLGUZLTUFP-UHFFFAOYSA-N 0.000 claims description 2
- PXMJANKVYIZZLE-UHFFFAOYSA-N dioxomolybdenum;dihydrofluoride Chemical compound F.F.O=[Mo]=O PXMJANKVYIZZLE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 claims description 2
- HCUBBWLKCMNCRQ-UHFFFAOYSA-N oxomolybdenum;tetrahydrofluoride Chemical compound F.F.F.F.[Mo]=O HCUBBWLKCMNCRQ-UHFFFAOYSA-N 0.000 claims description 2
- UXCDUFKZSUBXGM-UHFFFAOYSA-N phosphoric tribromide Chemical compound BrP(Br)(Br)=O UXCDUFKZSUBXGM-UHFFFAOYSA-N 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims 3
- 229910000416 bismuth oxide Inorganic materials 0.000 claims 2
- 229910016295 BiOF Inorganic materials 0.000 claims 1
- 239000008247 solid mixture Substances 0.000 claims 1
- CFJRPNFOLVDFMJ-UHFFFAOYSA-N titanium disulfide Chemical compound S=[Ti]=S CFJRPNFOLVDFMJ-UHFFFAOYSA-N 0.000 claims 1
- 239000010406 cathode material Substances 0.000 description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- 150000004694 iodide salts Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical class [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 235000006629 Prosopis spicigera Nutrition 0.000 description 1
- 240000000037 Prosopis spicigera Species 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910003092 TiS2 Inorganic materials 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000036760 body temperature Effects 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Chemical class [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- ICIWUVCWSCSTAQ-UHFFFAOYSA-N iodic acid Chemical class OI(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-N 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- PDWVXNLUDMQFCH-UHFFFAOYSA-N oxoantimony;hydrochloride Chemical compound Cl.[Sb]=O PDWVXNLUDMQFCH-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- H01M4/58—Selection 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
-
- 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
- H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- 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)
- Primary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Conductive Materials (AREA)
- Secondary Cells (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
SOLID STATE CELL WITH HALOGEN-CHALCOGEN-METAL SOLID CATHODE ABSTRACT A solid state electrochemical cell containing a cathode comprising a compound which is solid at ambient temperatures and which contains a halogen atom, a chalcogen atom and an atom of a third element, with the chalcogen and halogen not in a radical grouping.
Description
Z312 ~3 3324-~
This invention relates to novel cathode materials for solid state cells, and more particularly it relates to novel cathode materials for high energy density, solid state cells.
With the increased sophistication of components in electronic devices, such as the recent progression from transis-tors to miniature integrated circuits, the operating power demands of these devices have been drastically reduced. Thus, some devices such as pacemakers no longer operate at drain rates measured in milliamperes but rather they operate at drain rates measured in microamperes. As a direct result thereof, solid state electrochemical cells with high voltages and high energy density but generally capable of operating only in the micro-ampere drain region have become of increasingly greater importance.
This is especially true because of their extremely important ability to remain stable. Solid state cells have shelf lives in excess of lO years and are not subject to~detrimental gassing and leakage such as can be found in solution cells. Additionally, they are stably operable under widely varying temperature condi-tions.
. . .~, . .
Low energy density solid state cells such as the ~; Ag/RbAg4IsiRbI3 cells of the prior art, while capable of delivering energy at a discharge rate of 40 milliamps at room temperature have an energy density of less than 1 Whr/in3, and discharge at a low voltage of about 0.6 volts. Devices such as pacemakers will require frequent complicated replacement.
,,~
'-~
, . : , ; .. ~ ~
11~6232 3324~E
. .
~ells have been developed which can provide a voltage in excess of 1.5 volts and which have energy densities ranging up to about 10 whr/in3 for erfective lony term operation under low drain rate applications. These cells generally employ lithium metal anodes, lithium halide electrolytes (most notably lithium iodide) and cathodes of heavy metal halides (particularly iodides), sulfides, or iodine itsel~.
It is an object of the prese,nt invention to provide solid cathode materials of high energy density which are par-ticularly use~ul for long life, high energy density, solid state cell systems. A further object of the invention is to provide solid cathode materials which are useful for e~tended life low energy density high drain rate solid state cells.
The materials used in the cathodes o~ the present in-vention have as their basis, compounds having at least one atom from the chalcogen family (Group VIA of the Periodic Table) which includes oxygen, sulfur, selenium and tellurium and at least one atom from the halogen family (Group VIIA of the Periodic Table) i.e. fluorine, chlorine, bromine and iodine ~ ; .
i~` and which will be referred to herein as "halo-chalcogenides."
``, Since the above ca~hode materials are components in solid state cells the compounds must be solid at room ( or ambient) temper-" ature. Additionally, the halogen and chalcogen should be iden-; A~
ti~iable as separate entities within the compound and not as combined radical groupings such as chlorates, bromates or iodates.
` The halogen and chalcogen are combined in a compound with a third element, usually a metal such as bismuth or molybdenum or a non-metal such as phosphorus.
, . ~
.- .
1;;23Z
According to a broad aspect of the present invention there is provided a solid state electrochemical . cell comprising a solid anode, a solid electrolyte and a . cathode comprising a compound which is solid at ambient `,''.
~ temperatures and which contains at least one halogen atom, .~ at least one c'nalcogen atom, and at least one atom of a .' third element selected from the group consisting of As, ~` Bi, Mo, Nb, P, Sb, and Se. The-halogen and the chalcogen i; are separately identifiable in a state other than a ~ 10 radical grouping.
~ .~
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;`;~',' '`~' `
i~'~'"
~ ~, ~,, .
;.`'~
'~`"'` ~, ,'`'~i ~ 2a -, ~ ~ ~ ~ 3324-E
The preferred chalcogen is oxygen and the preferred halogen is iodine. Acordingly, oxide iodides such as bismuth oxide iodide are most preferred.
Other iodo-chalcogenides include BiTeI, BiSI, BiSeI, and SbSI.
Examples of oxide halides, other than oxide-iodides, include AsOCl, BiOBr, BiOCl, BioF, MoO2Br2, MoOC13, MoO2C12 MoOC14, MoOF4, MoO2F2, NbOBr3, N~OC13" POBr3, P404Cllo, Sb405C1 SbOCl, and SeOBr2.
Compounds having chalcogens other than oxygen and halogens other than iodine include t'~e following halo-chalcogen-ides: SeBrC13 and SeBr3Cl.
These solid halo-chalcogenides, while useful with generally any conventiQnal anode material, are particularly .:
~ .
'~ useful in long lifetime applications which require greater energy . ~ , `' density using cells h~ving anodes selected from Groups IA and .~
` IIA of the Periodic Table and other metals above hydrogen in f the EMF scale. Of particular interest is the lithi~ anode ,~ which, because of its light weight and high voltage, provides :
t~ greatest energy density.
~` Electrolytes used in high energy density solid state ;
` cell are generally composed of alkali metal salts and particularly alkali metal halides, with the preferred electrolyte in solid . .
state cells belng lithium iodide because of its relatively i~ high ionic conductivity and low electronic conductivity. The ~` conductivity of lithium iodide electrolytes have been improved .
by the add1tion of aluminum oxide (A1203) and lithium hydroxide (LioH) as more ~ully set forth in U.S. patent no. 3,713,897 and this electrolyte is therefore presently preferred.
. ~ .
1~16Z3~ 3324-E
` The following examples clearly show the benefic~al ;, er~ects of the novel solid cathode materials o~ the present in~
vention. The examples are set forth primarily for illustrati~e purposes and any specifics contained therein should not be considered as limitations on the inventive concept. All parts in the examples, as throughout the specification and claims, are parts by weight unless otherwise indicated.
EX~MPLE 1 ~, .
A solid state cell is made with a lithium metal disc having a contact surface area of about 2 cm2; and a thickness of 0.01 cm; a solid electrolyte disc with a surface area on each side of about 2.38 cm2 and consisting of LiI, LioH and A12O3 (LLA) in a 4:1:2 ratio; and a cathode disc weighing 200 mg, comprising 60~/o BiOI and 40% bismuth as conductive material and having a surface in contact with said electrolyte of about
This invention relates to novel cathode materials for solid state cells, and more particularly it relates to novel cathode materials for high energy density, solid state cells.
With the increased sophistication of components in electronic devices, such as the recent progression from transis-tors to miniature integrated circuits, the operating power demands of these devices have been drastically reduced. Thus, some devices such as pacemakers no longer operate at drain rates measured in milliamperes but rather they operate at drain rates measured in microamperes. As a direct result thereof, solid state electrochemical cells with high voltages and high energy density but generally capable of operating only in the micro-ampere drain region have become of increasingly greater importance.
This is especially true because of their extremely important ability to remain stable. Solid state cells have shelf lives in excess of lO years and are not subject to~detrimental gassing and leakage such as can be found in solution cells. Additionally, they are stably operable under widely varying temperature condi-tions.
. . .~, . .
Low energy density solid state cells such as the ~; Ag/RbAg4IsiRbI3 cells of the prior art, while capable of delivering energy at a discharge rate of 40 milliamps at room temperature have an energy density of less than 1 Whr/in3, and discharge at a low voltage of about 0.6 volts. Devices such as pacemakers will require frequent complicated replacement.
,,~
'-~
, . : , ; .. ~ ~
11~6232 3324~E
. .
~ells have been developed which can provide a voltage in excess of 1.5 volts and which have energy densities ranging up to about 10 whr/in3 for erfective lony term operation under low drain rate applications. These cells generally employ lithium metal anodes, lithium halide electrolytes (most notably lithium iodide) and cathodes of heavy metal halides (particularly iodides), sulfides, or iodine itsel~.
It is an object of the prese,nt invention to provide solid cathode materials of high energy density which are par-ticularly use~ul for long life, high energy density, solid state cell systems. A further object of the invention is to provide solid cathode materials which are useful for e~tended life low energy density high drain rate solid state cells.
The materials used in the cathodes o~ the present in-vention have as their basis, compounds having at least one atom from the chalcogen family (Group VIA of the Periodic Table) which includes oxygen, sulfur, selenium and tellurium and at least one atom from the halogen family (Group VIIA of the Periodic Table) i.e. fluorine, chlorine, bromine and iodine ~ ; .
i~` and which will be referred to herein as "halo-chalcogenides."
``, Since the above ca~hode materials are components in solid state cells the compounds must be solid at room ( or ambient) temper-" ature. Additionally, the halogen and chalcogen should be iden-; A~
ti~iable as separate entities within the compound and not as combined radical groupings such as chlorates, bromates or iodates.
` The halogen and chalcogen are combined in a compound with a third element, usually a metal such as bismuth or molybdenum or a non-metal such as phosphorus.
, . ~
.- .
1;;23Z
According to a broad aspect of the present invention there is provided a solid state electrochemical . cell comprising a solid anode, a solid electrolyte and a . cathode comprising a compound which is solid at ambient `,''.
~ temperatures and which contains at least one halogen atom, .~ at least one c'nalcogen atom, and at least one atom of a .' third element selected from the group consisting of As, ~` Bi, Mo, Nb, P, Sb, and Se. The-halogen and the chalcogen i; are separately identifiable in a state other than a ~ 10 radical grouping.
~ .~
! ':
.,.
.' ~`}
~` ',~,. "~
'`,` `
` ~I` `.
.,;`' :
;`;~',' '`~' `
i~'~'"
~ ~, ~,, .
;.`'~
'~`"'` ~, ,'`'~i ~ 2a -, ~ ~ ~ ~ 3324-E
The preferred chalcogen is oxygen and the preferred halogen is iodine. Acordingly, oxide iodides such as bismuth oxide iodide are most preferred.
Other iodo-chalcogenides include BiTeI, BiSI, BiSeI, and SbSI.
Examples of oxide halides, other than oxide-iodides, include AsOCl, BiOBr, BiOCl, BioF, MoO2Br2, MoOC13, MoO2C12 MoOC14, MoOF4, MoO2F2, NbOBr3, N~OC13" POBr3, P404Cllo, Sb405C1 SbOCl, and SeOBr2.
Compounds having chalcogens other than oxygen and halogens other than iodine include t'~e following halo-chalcogen-ides: SeBrC13 and SeBr3Cl.
These solid halo-chalcogenides, while useful with generally any conventiQnal anode material, are particularly .:
~ .
'~ useful in long lifetime applications which require greater energy . ~ , `' density using cells h~ving anodes selected from Groups IA and .~
` IIA of the Periodic Table and other metals above hydrogen in f the EMF scale. Of particular interest is the lithi~ anode ,~ which, because of its light weight and high voltage, provides :
t~ greatest energy density.
~` Electrolytes used in high energy density solid state ;
` cell are generally composed of alkali metal salts and particularly alkali metal halides, with the preferred electrolyte in solid . .
state cells belng lithium iodide because of its relatively i~ high ionic conductivity and low electronic conductivity. The ~` conductivity of lithium iodide electrolytes have been improved .
by the add1tion of aluminum oxide (A1203) and lithium hydroxide (LioH) as more ~ully set forth in U.S. patent no. 3,713,897 and this electrolyte is therefore presently preferred.
. ~ .
1~16Z3~ 3324-E
` The following examples clearly show the benefic~al ;, er~ects of the novel solid cathode materials o~ the present in~
vention. The examples are set forth primarily for illustrati~e purposes and any specifics contained therein should not be considered as limitations on the inventive concept. All parts in the examples, as throughout the specification and claims, are parts by weight unless otherwise indicated.
EX~MPLE 1 ~, .
A solid state cell is made with a lithium metal disc having a contact surface area of about 2 cm2; and a thickness of 0.01 cm; a solid electrolyte disc with a surface area on each side of about 2.38 cm2 and consisting of LiI, LioH and A12O3 (LLA) in a 4:1:2 ratio; and a cathode disc weighing 200 mg, comprising 60~/o BiOI and 40% bismuth as conductive material and having a surface in contact with said electrolyte of about
2.38 cm2. The cell is constructed as a cathode limited cell, , i .
~'~ as follows. The electrolyte is pressed first with the cathode ~`~ at a pressure of about 100,05C pSl. Thereafter, the anode is pressed to the opposite side of the electrolyte using a pressure ..:
; of about 50,000 psi. The cell, when discharged at 37 C under a load of 200 k~, started discharging at 2 volts and after ~ 2400 hours is still discharging at 1.4 volts.
'~ EXAMPLE 2 I
- Several solid state cells are made in accordance with the procedures of Example 1 but with the cathodes comprising 33~/O BiOI, 33~O LLA and 33% bismuth with the latter two compo--4- ;
~6Z3~ 3324-~
~.~
' nents added for conductivity purposes. Three cells are dis-charged at llooc under loads of 1) 7.5 ~) 10 k~v and 3) 5 k ~
with the following results in terms of cell capacity. (Initial voltage for all three cells is 2.4 V.) cell load mAhrs to 2.0 V 1.5 V 1.0 V
`~ 17.5 k~3 12.5 20 ~ 21.5 210 k~ 13.5 19.5 ~21.5 35 k~ 11.5 ,18 ~20 A solid state cell is made in accordance with the procedure of Example 1 but with the cathode and electrolyte . having surface areas of 2.25 cm2 and the cathode comprises 60%
;:` BiOI and 40% bismuthO The cell is discharged at 110C under a ,!' load of 10 k~. After reaching 2.0 volts from a initial voltage of about 2.2 volts the cell output is about 3 mAhr. The cell has a capacity output of about 38 mAhrs to l.S volts and about ., ~` 45 mAhr to 1 volt.
'"~ .
~. E,YAMPLE 4 : ~, A cell is made in accordance with the procedure as in Example 1 but with a cathode comprising 90% BiOI and 10% of an 80:20 mi~ture of TiS2 and S. The cell is discharged at 37 C
(normal body temperature) under a load of 200k~. The initial voltage of the cell is about 2.3 volts and the cell is still , `~ discharging at about 1.9 volts after 2400 hours.
.; . . - . ~
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. .
. ~
: Several cells are made in accordance with the proce-.' dure as in Example 4 but with a surface area of cathode and electrolyte of about 2.25 cm2. Three cells are discharged at ~.q `~; 110C under loads of 1) 5 k.n.,2) 8 k:~Jand 3) lOk~ respectively, ~ . .
;~ with the following results in terms of cell capacity:
cell no. load initial volta~e m~hr to 2.0 volts to 1.5 volts 1 5k~ 2.5 18 53 ` 2 8k~ 2.6 33 54
~'~ as follows. The electrolyte is pressed first with the cathode ~`~ at a pressure of about 100,05C pSl. Thereafter, the anode is pressed to the opposite side of the electrolyte using a pressure ..:
; of about 50,000 psi. The cell, when discharged at 37 C under a load of 200 k~, started discharging at 2 volts and after ~ 2400 hours is still discharging at 1.4 volts.
'~ EXAMPLE 2 I
- Several solid state cells are made in accordance with the procedures of Example 1 but with the cathodes comprising 33~/O BiOI, 33~O LLA and 33% bismuth with the latter two compo--4- ;
~6Z3~ 3324-~
~.~
' nents added for conductivity purposes. Three cells are dis-charged at llooc under loads of 1) 7.5 ~) 10 k~v and 3) 5 k ~
with the following results in terms of cell capacity. (Initial voltage for all three cells is 2.4 V.) cell load mAhrs to 2.0 V 1.5 V 1.0 V
`~ 17.5 k~3 12.5 20 ~ 21.5 210 k~ 13.5 19.5 ~21.5 35 k~ 11.5 ,18 ~20 A solid state cell is made in accordance with the procedure of Example 1 but with the cathode and electrolyte . having surface areas of 2.25 cm2 and the cathode comprises 60%
;:` BiOI and 40% bismuthO The cell is discharged at 110C under a ,!' load of 10 k~. After reaching 2.0 volts from a initial voltage of about 2.2 volts the cell output is about 3 mAhr. The cell has a capacity output of about 38 mAhrs to l.S volts and about ., ~` 45 mAhr to 1 volt.
'"~ .
~. E,YAMPLE 4 : ~, A cell is made in accordance with the procedure as in Example 1 but with a cathode comprising 90% BiOI and 10% of an 80:20 mi~ture of TiS2 and S. The cell is discharged at 37 C
(normal body temperature) under a load of 200k~. The initial voltage of the cell is about 2.3 volts and the cell is still , `~ discharging at about 1.9 volts after 2400 hours.
.; . . - . ~
., ~`.' ~ ~1 ~ ;, ~ 6Z3Z 3324-E
. .
. ~
: Several cells are made in accordance with the proce-.' dure as in Example 4 but with a surface area of cathode and electrolyte of about 2.25 cm2. Three cells are discharged at ~.q `~; 110C under loads of 1) 5 k.n.,2) 8 k:~Jand 3) lOk~ respectively, ~ . .
;~ with the following results in terms of cell capacity:
cell no. load initial volta~e m~hr to 2.0 volts to 1.5 volts 1 5k~ 2.5 18 53 ` 2 8k~ 2.6 33 54
3 lOk~ 2.6 34 55 The foregoing examples are illustrative of the inven-tion. It is understood that various cell constructions as well as changes in component ratios and compositions can be made with-out departing from the scope of the present invention as defined in the following claims.
.
.~ .
;~ ~
! `
``;' ~. . .
---_ .
; -6-
.
.~ .
;~ ~
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``;' ~. . .
---_ .
; -6-
Claims (16)
1. A solid state electrochemical cell comprising a solid anode, a solic electrolyte and a cathode comprising a compound which is solid at ambient temperatures and which contains at least one halogen atom, at least one chal-cogen atom, and at least one atom of a third element selected from the group consisting of As, Bi, Mo, Nb, P, Sb, and Se and wherein said halogen and said chalcogen are separately identifiable in a state other than a radical grouping.
2. A solid state cell as in claim 1 wherein said cathode further includes conductive materials.
3. A solid state cell as in claim 1 wherein said halogen is iodine.
4. A solid state cell as in claim 1 wherein said chalcogen is oxygen.
5. A solid state cell as in claim 1 wherein said anode is a metal above hydrogen in the EMF scale.
6. A solid state cell as in claim 5 wherein said anode is lithium.
7. A solid state cell as in claim 6 wherein said solid electrolyte includes an alkali metal salt.
8. A solid state cell as in claim 7 wherein said alkali metal salt is lithium iodide.
9. A solid state electrochemical cell comprising a solid anode, a solid electrolyte and a cathode comprising a bismuth oxide halide.
10. A solid state cell as in claim 9 wherein said solid anode is comprised of lithium.
11. A solid state cell as in claim 10 wherein said solid electrolyte is comprised of an alkali metal salt.
12. A solid state electrochemical cell comprising a solid anode, a solid electrolyte and a cathode comprising bismuth oxide iodide.
13. A solid state electrochemical cell comprising a solid anode comprised of lithium, a solid electrolyte including lithium iodide and a solid cathode comprised of bismuth oxide halide.
14. A solid state cell as in claim 13 wherein said compound is bismuth oxide iodide.
15. A solid state cell as in claim 14 wherein said cathode further includes a conductive material selected from the group consisting of bismuth, titanium disulfide, said solid electrolyte and mixtures thereof.
16. A solid state electrochemical cell comprising a solid anode, a solid electrolyte and a cathode comprising a compound selected from the group consisting of AsOCl, BiOBr, BiOCl, BiOF, BiOI, BiSI, BiSeI, BiTeI, MoO2Br2, MoOCl3, MoO2C12, MoOC14, MoOF4, MoO2F2, NbOBr3, NbOC13, POBr3, P4O4C110, Sb4O5C12, SbOC1, SbSI, and SeOBr2.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US821,885 | 1977-08-05 | ||
| US05/821,885 US4127708A (en) | 1977-08-05 | 1977-08-05 | Solid state cell with halogen-chalcogen-metal solid cathode |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1116232A true CA1116232A (en) | 1982-01-12 |
Family
ID=25234523
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA308,563A Expired CA1116232A (en) | 1977-08-05 | 1978-08-01 | Solid state cell with halogen-chalcogen-metal solid cathode |
Country Status (13)
| Country | Link |
|---|---|
| US (1) | US4127708A (en) |
| JP (1) | JPS5429026A (en) |
| BE (1) | BE869508A (en) |
| CA (1) | CA1116232A (en) |
| CH (1) | CH637790A5 (en) |
| DE (1) | DE2833985A1 (en) |
| DK (1) | DK345978A (en) |
| FR (1) | FR2399742A1 (en) |
| GB (1) | GB2025113B (en) |
| IL (1) | IL55230A (en) |
| IT (1) | IT1097630B (en) |
| NL (1) | NL7808201A (en) |
| SE (1) | SE7808406L (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2849294C3 (en) * | 1977-11-22 | 1982-03-04 | Asahi Kasei Kogyo K.K., Osaka | Thin metal halide cell and process for its manufacture |
| US4317874A (en) * | 1980-10-24 | 1982-03-02 | Ray-O-Vac Corporation | Self healing cathodes |
| US6591133B1 (en) * | 2000-11-27 | 2003-07-08 | Microlin Llc | Apparatus and methods for fluid delivery using electroactive needles and implantable electrochemical delivery devices |
| US7947392B2 (en) * | 2004-10-01 | 2011-05-24 | Rutgers The State University of New Jersey, U.S. | Bismuth fluoride based nanocomposites as electrode materials |
| US8039149B2 (en) * | 2004-10-01 | 2011-10-18 | Rutgers, The State University | Bismuth oxyfluoride based nanocomposites as electrode materials |
| US20070025869A1 (en) * | 2005-07-15 | 2007-02-01 | Gordon John H | Fluid Delivery Device |
| US20080147186A1 (en) * | 2006-12-14 | 2008-06-19 | Joshi Ashok V | Electrochemical Implant For Delivering Beneficial Agents |
| US9692039B2 (en) | 2012-07-24 | 2017-06-27 | Quantumscape Corporation | Nanostructured materials for electrochemical conversion reactions |
| WO2015130831A1 (en) | 2014-02-25 | 2015-09-03 | Quantumscape Corporation | Hybrid electrodes with both intercalation and conversion materials |
| WO2016025866A1 (en) | 2014-08-15 | 2016-02-18 | Quantumscape Corporation | Doped conversion materials for secondary battery cathodes |
| JP7769933B2 (en) * | 2021-01-26 | 2025-11-14 | パナソニックＩｐマネジメント株式会社 | battery |
| CN120854662B (en) * | 2025-09-23 | 2025-11-25 | 深圳大学 | A high-valence metal-oxygen-chloride surface-modified inorganic solid electrolyte material, its preparation method and application |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2786088A (en) * | 1952-09-09 | 1957-03-19 | Sprague Electric Co | Electrochemical systems |
| US2809225A (en) * | 1954-04-21 | 1957-10-08 | Rca Corp | Primary cell |
| US3073884A (en) * | 1959-08-03 | 1963-01-15 | Ethyl Corp | High energy batteries |
| US3701686A (en) * | 1966-02-11 | 1972-10-31 | North American Rockwell | Solid state cell construction |
| US3701685A (en) * | 1970-07-21 | 1972-10-31 | North American Rockwell | Process for a solid state cell by spraying with an organic solvent |
| US3730775A (en) * | 1971-07-09 | 1973-05-01 | Mallory & Co Inc P R | Tin halide cathode for solid electrolyte batttery systems |
| JPS4844500A (en) * | 1971-10-12 | 1973-06-26 | ||
| US3791867A (en) * | 1972-07-24 | 1974-02-12 | Bell Telephone Labor Inc | Rechargable nonaqueous battery |
| FR2196293B1 (en) * | 1972-08-18 | 1975-03-07 | Armand Michel | |
| US3988164A (en) * | 1974-04-25 | 1976-10-26 | P. R. Mallory & Co., Inc. | Cathode material for solid state batteries |
| US3953229A (en) * | 1975-03-12 | 1976-04-27 | General Electric Company | Sealed lithium-reducible phosphorous oxyhalide cell |
| US4049887A (en) * | 1976-07-20 | 1977-09-20 | Exxon Research & Engineering Co. | Electrochemical cells with cathode-active materials of layered compounds |
| FR2376077A1 (en) * | 1976-12-31 | 1978-07-28 | Anvar | Insertion cpd. prepn. from halide with lamellar structure - used as electrode material for electrochemical generator |
-
1977
- 1977-08-05 US US05/821,885 patent/US4127708A/en not_active Expired - Lifetime
-
1978
- 1978-07-27 IL IL55230A patent/IL55230A/en unknown
- 1978-08-01 CA CA308,563A patent/CA1116232A/en not_active Expired
- 1978-08-03 DE DE19782833985 patent/DE2833985A1/en not_active Ceased
- 1978-08-04 DK DK345978A patent/DK345978A/en not_active Application Discontinuation
- 1978-08-04 SE SE7808406A patent/SE7808406L/en unknown
- 1978-08-04 CH CH833878A patent/CH637790A5/en not_active IP Right Cessation
- 1978-08-04 FR FR7823172A patent/FR2399742A1/en active Granted
- 1978-08-04 NL NL787808201A patent/NL7808201A/en not_active Application Discontinuation
- 1978-08-04 BE BE2057197A patent/BE869508A/en not_active IP Right Cessation
- 1978-08-05 JP JP9575778A patent/JPS5429026A/en active Pending
- 1978-08-07 GB GB7832476A patent/GB2025113B/en not_active Expired
- 1978-08-07 IT IT26547/78A patent/IT1097630B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| NL7808201A (en) | 1979-02-07 |
| IL55230A0 (en) | 1978-09-29 |
| BE869508A (en) | 1978-12-01 |
| FR2399742B1 (en) | 1984-06-08 |
| CH637790A5 (en) | 1983-08-15 |
| GB2025113B (en) | 1982-05-19 |
| GB2025113A (en) | 1980-01-16 |
| IL55230A (en) | 1982-02-28 |
| IT1097630B (en) | 1985-08-31 |
| US4127708A (en) | 1978-11-28 |
| SE7808406L (en) | 1979-02-06 |
| IT7826547A0 (en) | 1978-08-07 |
| DE2833985A1 (en) | 1979-02-22 |
| DK345978A (en) | 1979-02-06 |
| FR2399742A1 (en) | 1979-03-02 |
| JPS5429026A (en) | 1979-03-03 |
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