CA1199679A - High energy ambient temperature inorganic electrochemical power cell - Google Patents
High energy ambient temperature inorganic electrochemical power cellInfo
- Publication number
- CA1199679A CA1199679A CA000440416A CA440416A CA1199679A CA 1199679 A CA1199679 A CA 1199679A CA 000440416 A CA000440416 A CA 000440416A CA 440416 A CA440416 A CA 440416A CA 1199679 A CA1199679 A CA 1199679A
- Authority
- CA
- Canada
- Prior art keywords
- ambient temperature
- high energy
- power cell
- calcium
- temperature inorganic
- 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
Classifications
-
- 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
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Primary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
ABSTRACT
A high energy ambient temperature inorganic electro-chemical power cell is provided comprising calcium metal alloyed with about 10 percent of either zinc or antimony as the anode, high surface area carbon black as the cathode and a solution of calcium tetrachloroaluminate or lithium tetrachloroaluminate in sulfuryl chloride or thionyl chloride as the electrolyte.
A high energy ambient temperature inorganic electro-chemical power cell is provided comprising calcium metal alloyed with about 10 percent of either zinc or antimony as the anode, high surface area carbon black as the cathode and a solution of calcium tetrachloroaluminate or lithium tetrachloroaluminate in sulfuryl chloride or thionyl chloride as the electrolyte.
Description
~9~7~
This invention relates in general to the use of calcium alloy anod~s in high energy amhient temp~rature inorganic electrochemical power c~lls and in particular to the use of calcium me~al alloyed with either 10 percent ~inc or antimony as the anode in a high energy ambient temperature inorganic electrochemical power cell including high surface area carbon black as the cathode and a solution o calcium tetrachloroaluminate .in suluryl chloride as the electrolyte.
~mbient temperature inorganic electrolyte cells have generally employed li~hiu~ metal as the anode, hi~h surf~ce area carbon blacl~ as the cathode and a soïution of lith.ium tetrachloroaluminate in thionyl chloride or sulfuryl chloride as the electrolyteO ~owever, due to the low melting point of lithium metal ~180~7 degrees C~ the lithium metal anode can melt under conditi4n~ when exc~ssive heat is generated such as short circuit, forced overdischarget etc. Molten lithium metal then can react with other components o the cell or discharge products such as elemental sulfur causing cell ventin~, cell ~upture or under worst conditions cell e~plosionsl Attempts are~ therefore, bein~ made to find alternate anode materials for these cells~ ThusJ calcium metal which has a high n~elting point (~39 degrees C) has been success-fully used as the anode material in calciumithionyl chloride and calcium~sulfuryl chloride cell80 The difficulty however~
is ~hat th~ open circuit voltage of calcium-sulfuryl chloride cells ~ 302 volts) is much lo~er than the theoretically cal-culated value of 30807 volts from the thermodynamic ~ataO
Thl~S ~ calcillmIsul~uryl chloride cells vperate much below th~ir ~lleore~:ical poten~ial because o possible slow electro~
chemical kinet.i~s of th~ calcillm ele~rode~
The general object of this invention is to prov.ide an ir,~proved high en~ryy amb.ient temperature electrochemical po~er cell, A more particu~ar object of the inventiorl is to provide an improvment on the calciu~ anode used in calci-lm-sul furyl chloride cells.
It has now been found ~ha~ the foregoing objects can be ob~ained by alloying the calcium metal with about 10 percent zinc or antimon~
The use of the calcium-zinc alloy or the calcium-antimony alloy as anodes in calcium~'sul~u~yl chloride cells improves the electrochemical kinetic~ o~ ~he calcium elec~rodes result.ing in lo~er polari~,a~ion and improved rate capability of calcium~sulfu~yl chloride cell~O
The ~ac~ tha~c the calciuin~inc and calcium-an~imony ~lloy ~Jould work so well was unea~pected and unp~edictableO
l~his was established when ~sevelal alloys were tes~ed as anode materials. These alloys includedO calcium-lo% Magnesium~
~alcium - 10~ Tin, Calcium -10% Cadmium~ Calcium ~ 10~ Aluminum, ~alciu~l~10~ Zinc and Calcium-10% Antimony~ Onl~ the calci~nl-lo%
zinc and Calcium~1~% Antimony showed be~ter performance than the calcium metalO
DESCRIPTION OF T~E ~WING
The anodic polari2at.ion curves or the seve~al alloys ~ested as anode material~ are plotted in the drawing~
It is seen that except for c~lcium-zinc and calcium-ant.imony~ all o~her alloy~ have poorer perormance than the calci~m met~l anode~ Both calcium-zînc and calcium-~ntimony show be~ter p~rformance than ~he calcium metal, The împrove-mcnt achi~ved with calcium-lo% antimony is especially signi-ficantO
The calcium~10~ zinc alloy anode and the calcium-10~
antimony alloy anode is prepared by art established tech-nique generally i~volving the melting of 90 weight percent calcium and 10 weight percent ZillC or antimony under inert atmosphere o argon gas or under vacuum and then resolidi-fication of the homogeneous mixture under the inert atmos-phere.
In preparing a complete cell, a cathode is first prepar-ed u~ing art established techniques. ~lore particularly,a cathode may be conveniently prepared by mixing one gram of a furnace black carbon powder having a surface area of about 1000 square meters per gram with an emulsion containing 0.12 grams of polytetra~luoroethylene and a su~ficient a~ount of wa~er to yield a sti~f paste. The paste is then applied to a ~5 cm x 2 cln expanded nickel support screen, The support is prepared by welding 2 thicknesses of screen to-gether, with the mesh ou~ of registration so as ~o provide maximum tortuosity. ~Yhile still moist, the electrode is compressed to an intermediate thickness o~ 0~0615 inch.
After Yacuum dry-ng for 24 hours at 99 degrees C, the cathode is compressed in a 0.025 inch ~rame and a~er re-expansion has a final thickness of 0.035 inch. The cathode has a porosity of 87 percent~
A complete cell can be conveniently assembled in an all-Teflon*jig with the plane of the electrodes parallel to the bottom of the jig. The cathode as prepared above is placed between two calcium -10~ antimony alloy anodes.
After assembling the c~ll and adding 3cc of a 004 molar solution of calciu~ tet~achloroaluminate in sulfuryl chloride as the electrolyte~ a leflon weight is applied to the cell to help ~aint~in good contact between the cell components.
In lieu of ~rnace black carbon powder as the high surface area carbon black one may use other high surface area carbon blac~s~
* denotes trade mark.
~ .n l.ieu of calcium tetrachloroalumillate as the elec~
trolyte s~ltp on~ m~y u~ lith.ium t~tLachloro~lumlnate or tetraalkyl sal.tsO
In lieu of sulfuryl chloride as the elecLrolyte solvent, orle ~ay use thionyl chloride or modify the electrolyte by adding an inorgan.i.c solvellt sucb as phosphorus oxychloride and such organic solven~s as propylene carbonate, acetonitrilep etc~ These solYellts are added ~o modi~y the physiochem.ical proper~ies o~ the electrolyte such ~5 the lo conductivity~ boilin~ pointt free~ing pointO vapor pressurep etcO
This invention relates in general to the use of calcium alloy anod~s in high energy amhient temp~rature inorganic electrochemical power c~lls and in particular to the use of calcium me~al alloyed with either 10 percent ~inc or antimony as the anode in a high energy ambient temperature inorganic electrochemical power cell including high surface area carbon black as the cathode and a solution o calcium tetrachloroaluminate .in suluryl chloride as the electrolyte.
~mbient temperature inorganic electrolyte cells have generally employed li~hiu~ metal as the anode, hi~h surf~ce area carbon blacl~ as the cathode and a soïution of lith.ium tetrachloroaluminate in thionyl chloride or sulfuryl chloride as the electrolyteO ~owever, due to the low melting point of lithium metal ~180~7 degrees C~ the lithium metal anode can melt under conditi4n~ when exc~ssive heat is generated such as short circuit, forced overdischarget etc. Molten lithium metal then can react with other components o the cell or discharge products such as elemental sulfur causing cell ventin~, cell ~upture or under worst conditions cell e~plosionsl Attempts are~ therefore, bein~ made to find alternate anode materials for these cells~ ThusJ calcium metal which has a high n~elting point (~39 degrees C) has been success-fully used as the anode material in calciumithionyl chloride and calcium~sulfuryl chloride cell80 The difficulty however~
is ~hat th~ open circuit voltage of calcium-sulfuryl chloride cells ~ 302 volts) is much lo~er than the theoretically cal-culated value of 30807 volts from the thermodynamic ~ataO
Thl~S ~ calcillmIsul~uryl chloride cells vperate much below th~ir ~lleore~:ical poten~ial because o possible slow electro~
chemical kinet.i~s of th~ calcillm ele~rode~
The general object of this invention is to prov.ide an ir,~proved high en~ryy amb.ient temperature electrochemical po~er cell, A more particu~ar object of the inventiorl is to provide an improvment on the calciu~ anode used in calci-lm-sul furyl chloride cells.
It has now been found ~ha~ the foregoing objects can be ob~ained by alloying the calcium metal with about 10 percent zinc or antimon~
The use of the calcium-zinc alloy or the calcium-antimony alloy as anodes in calcium~'sul~u~yl chloride cells improves the electrochemical kinetic~ o~ ~he calcium elec~rodes result.ing in lo~er polari~,a~ion and improved rate capability of calcium~sulfu~yl chloride cell~O
The ~ac~ tha~c the calciuin~inc and calcium-an~imony ~lloy ~Jould work so well was unea~pected and unp~edictableO
l~his was established when ~sevelal alloys were tes~ed as anode materials. These alloys includedO calcium-lo% Magnesium~
~alcium - 10~ Tin, Calcium -10% Cadmium~ Calcium ~ 10~ Aluminum, ~alciu~l~10~ Zinc and Calcium-10% Antimony~ Onl~ the calci~nl-lo%
zinc and Calcium~1~% Antimony showed be~ter performance than the calcium metalO
DESCRIPTION OF T~E ~WING
The anodic polari2at.ion curves or the seve~al alloys ~ested as anode material~ are plotted in the drawing~
It is seen that except for c~lcium-zinc and calcium-ant.imony~ all o~her alloy~ have poorer perormance than the calci~m met~l anode~ Both calcium-zînc and calcium-~ntimony show be~ter p~rformance than ~he calcium metal, The împrove-mcnt achi~ved with calcium-lo% antimony is especially signi-ficantO
The calcium~10~ zinc alloy anode and the calcium-10~
antimony alloy anode is prepared by art established tech-nique generally i~volving the melting of 90 weight percent calcium and 10 weight percent ZillC or antimony under inert atmosphere o argon gas or under vacuum and then resolidi-fication of the homogeneous mixture under the inert atmos-phere.
In preparing a complete cell, a cathode is first prepar-ed u~ing art established techniques. ~lore particularly,a cathode may be conveniently prepared by mixing one gram of a furnace black carbon powder having a surface area of about 1000 square meters per gram with an emulsion containing 0.12 grams of polytetra~luoroethylene and a su~ficient a~ount of wa~er to yield a sti~f paste. The paste is then applied to a ~5 cm x 2 cln expanded nickel support screen, The support is prepared by welding 2 thicknesses of screen to-gether, with the mesh ou~ of registration so as ~o provide maximum tortuosity. ~Yhile still moist, the electrode is compressed to an intermediate thickness o~ 0~0615 inch.
After Yacuum dry-ng for 24 hours at 99 degrees C, the cathode is compressed in a 0.025 inch ~rame and a~er re-expansion has a final thickness of 0.035 inch. The cathode has a porosity of 87 percent~
A complete cell can be conveniently assembled in an all-Teflon*jig with the plane of the electrodes parallel to the bottom of the jig. The cathode as prepared above is placed between two calcium -10~ antimony alloy anodes.
After assembling the c~ll and adding 3cc of a 004 molar solution of calciu~ tet~achloroaluminate in sulfuryl chloride as the electrolyte~ a leflon weight is applied to the cell to help ~aint~in good contact between the cell components.
In lieu of ~rnace black carbon powder as the high surface area carbon black one may use other high surface area carbon blac~s~
* denotes trade mark.
~ .n l.ieu of calcium tetrachloroalumillate as the elec~
trolyte s~ltp on~ m~y u~ lith.ium t~tLachloro~lumlnate or tetraalkyl sal.tsO
In lieu of sulfuryl chloride as the elecLrolyte solvent, orle ~ay use thionyl chloride or modify the electrolyte by adding an inorgan.i.c solvellt sucb as phosphorus oxychloride and such organic solven~s as propylene carbonate, acetonitrilep etc~ These solYellts are added ~o modi~y the physiochem.ical proper~ies o~ the electrolyte such ~5 the lo conductivity~ boilin~ pointt free~ing pointO vapor pressurep etcO
Claims (18)
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A high energy ambient temperature inorganic electrochemical power cell comprising calcium metal alloyed with about 10 percent of an element selected from the group consisting of zinc and antimony as the anode, high surface area carbon black as the cathode and a solution of a salt selected from the group consisting of calcium tetrachloroaluminate and lithium tetrachloroaluminate in a solvent selected from the group consisting of sulfuryl chloride and thionyl chloride as the electrolyte .
2. A high energy ambient temperature inorganic electro-chemical power cell according to Claim 1 wherein the anode comprises calcium metal alloyed with about 10 percent of zinc.
3. A high energy ambient temperature inorganic electro-chemical power cell according to Claim 1 wherein the anode comprises calcium metal alloyed with about 10 percent of antimony.
4. A high energy ambient temperature inorganic electro-chemical power cell according to Claim 1 wherein the elec-trolyte is a solution of calcium tetrachloroaluminate in sulfuryl chloride.
5. A high energy ambient temperature inorganic electrochemical power cell according to Claim 2 wherein the electrolyte is a solution of calcium tetrachloroaluminate in sulfuryl chloride.
6. A high energy ambient temperature inorganic electrochemical power cell according to Claim 3 wherein the electrolyte is a solution of calcium tetrachloroaluminate in sulfuryl chloride.
7. A high energy ambient temperature inorganic electrochemical power cell according to Claim 1 wherein the electrolyte is a solution of calcium tetrachloroaluminate in thionyl chloride.
8. A high energy ambient temperature inorganic electrochemical power cell according to Claim 2 wherein the electrolyte is a solution of calcium tetrachloroaluminate in thionyl chloride.
9. A high energy ambient temperature inorganic electrochemical power cell according to Claim 3 wherein the electrolyte is a solution of calcium tetrachloroaluminate in thionyl chloride.
10. A high energy ambient temperature inorganic electrochemical power cell according to Claim 1 wherein the electrolyte is a solution of lithium tetrachloroaluminate in sulfuryl chloride.
11. A high energy ambient temperature inorganic electrochemical power cell according to Claim 1 wherein the electrolyte is a solution of lithium tetrachloroaluminate is sulfuryl chloride.
12. A high energy ambient temperature inorganic electrochemical power cell according to Claim 3 wherein the electrolyte is a solution of lithium tetrachloroaluminate in sulfuryl chloride.
13. A high energy ambient temperature inorganic electrochemical power cell according to Claim 1 wherein the electrolyte is a solution of lithium tetrachloroaluminate in thionyl chloride.
14. A high energy ambient temperature inorganic electrochemical power cell according to claim 2 wherein the electrolyte is a solution of lithium tetrachloroaluminate in thionyl chloride.
15. A high energy ambient temperature inorganic electrochemical power cell according to Claim 3 wherein the electrolyte is a solution of lithium tetrachloroaluminate in thionyl chloride.
16. An anode for use in a high energy ambient temperature inorganic electrochemical power cell, said anode comprising calcium metal alloyed with about 10% of an element selected from the group consisting of zinc and antimony.
17. An anode according to Claim 16 wherein the calcium metal is alloyed with about 10 percent antimony.
18. An anode according to Claim 16 wherein the calcium metal is alloyed with about 10 percent zinc.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/467,624 US4474863A (en) | 1983-02-18 | 1983-02-18 | High energy ambient temperature inorganic electrochemical power cell |
| US467,624 | 1990-01-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1199679A true CA1199679A (en) | 1986-01-21 |
Family
ID=23856440
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000440416A Expired CA1199679A (en) | 1983-02-18 | 1983-11-04 | High energy ambient temperature inorganic electrochemical power cell |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US4474863A (en) |
| CA (1) | CA1199679A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4543305A (en) * | 1983-10-24 | 1985-09-24 | The United States Of America As Represented By The Secretary Of The Army | Method of pretreating carbon black powder to improve cathode performance and lithium sulfuryl chloride cell including the pretreated carbon black powder |
| USH457H (en) | 1985-08-22 | 1988-04-05 | The United States Of America As Represented By The Secretary Of The Army | Cathode for use in high energy primary thionyl chloride cell systems and high energy primary thionyl chloride cell systems including the cathode |
| IL77786A (en) * | 1986-02-04 | 1990-02-09 | Univ Ramot | Electrochemical cell |
| TWI258239B (en) * | 2004-06-02 | 2006-07-11 | High Tech Battery Inc | Air electrode constituting multilayer sintered structure and manufacturing method thereof |
| US11901550B2 (en) | 2018-10-25 | 2024-02-13 | Northwestern University | Calcium-metal alloy anode materials for reversible calcium-ion batteries |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR407814A (en) * | 1900-01-01 | |||
| US3891457A (en) * | 1973-11-29 | 1975-06-24 | Gte Laboratories Inc | Electrochemical cell |
-
1983
- 1983-02-18 US US06/467,624 patent/US4474863A/en not_active Expired - Fee Related
- 1983-11-04 CA CA000440416A patent/CA1199679A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| US4474863A (en) | 1984-10-02 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |