CA1193654A - Catalytic cathode for primary and secondary fluid cathode depolarized cells - Google Patents
Catalytic cathode for primary and secondary fluid cathode depolarized cellsInfo
- Publication number
- CA1193654A CA1193654A CA000428679A CA428679A CA1193654A CA 1193654 A CA1193654 A CA 1193654A CA 000428679 A CA000428679 A CA 000428679A CA 428679 A CA428679 A CA 428679A CA 1193654 A CA1193654 A CA 1193654A
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- Prior art keywords
- cell
- cathode
- fluid
- group
- catalytic
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- 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
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Abstract
ABSTRACT
A fluid cathode depolarized cell having a catalytic cathode comprised of a graphite intercalated metal halide such as CuCl2, CoCl2, FeCl3 and SbF5.
A fluid cathode depolarized cell having a catalytic cathode comprised of a graphite intercalated metal halide such as CuCl2, CoCl2, FeCl3 and SbF5.
Description
~3~5~
This invention relates to primary and secondary non-aqueous fluid cathode depolarized cells particularly cells containing sulfur dioxide (S02) fluid cathode depolarizers.
Fluid cathode depolarized cells have generally contained inert carbon-aceous cathode or porous metals upon which the fluid cathode depolarizers are reduced during cell discharge. The porous metals were however somewhat unsatisfactory particularly at high rates because of their relatively low porosity when compared to the carbonaceous materials such as acetylene black and were therefore less preferred. The carbonaceous materials, while O satisfactory for primary cell application however suffered from degradation in secondary cells in which they were repeatedly expanded and contracted during the cell discharging and charging cycles respectively.
It is an object of the present invention to provide a fluld cathode depolarized cell with a catalytic cathode which is both highly porous and resistant to physical degradation.
It is a further object of the present invention to provide an effic-iently rechargeable S02 containing cell having such catalytic cathode.
These and other objects, features and advantages of the present inven-O tion will become more evident from the following discussion.
Generally the present invention comprises a non-aqueous fluid cathode depolarized cell with a catalytic cathode comprised of one or more graphite intercalated metal halides such as CuC12, CoC12, FeC13 and SbF5. Though graphite has generally been regarded as an unsuitable material for use as a cathode in fluid depolarized cells because of its tight lamellar structure, the graphite intercalated metal halides of the present invention have been found to be excellent porous cathode for fluid cathode depolarizer reduction in primary cell applications. Furthermore, cathodes made of the graphite intercalated metal halides of the present invention have been found to have a high degree of resiliency even under repeated expansion and contraction - during cycling in secondary cells. Thus the physical integrity of graphite 365~
intercalatedmetal halide cathodes is not seriously affected as compared to prior art carbonaceous cathodes generally used in rechargeable fluid cathode depolarized cells.
Some of the graphite intercalated~etal halides utilized in the cells of the present invention are, for example, commercially available under the Graphimet trademark (Alfa Division of Ventron Corp., Danvers, Mass.) and are generally 10 - 50% metal halide by weight. As opposed to simple mix-tures, the graphite intercalated metal halides are formed by reaction between the graphite and the metal halide whereby the lamellar structure of the graphite is opened to allow selective diffusion of molecules of proper spatial geometry therein. In the past, such graphite intercalated metal halides have been utilized as the actual active cathode materials of cells (U.S. patent no. 4.041,220 issued to Michel B. Armand). However, because of the very limited amount of reducible metal halide (50% or less) with such materials the capacity of such cells was very low. In contrast there-to the graphite intercalated metal halide cathode in the cell of the present invention i6 substantially inactive and serves as the catalytic site for the reduction of the high energy density fluid cathode depolari-zer.
The fluid cathode depolarizers utilized in the cell of the present invention include sulfur dioxide (SO2) which is utilizable in both primary and secondary cells. In secondary or rechargeable cells the sulfur dioxide is the sole electrolyte solvent since the further inclusion of organic cosolvents, as used in primary cells, reduces the cycling efficiencies with the production of generally irreversible reaction products. Thus, in the totally inorganic SO2 containing rechargeable cells only electrolytes such as gallium halide salts such as LiGaC14 or clovoborate salts such as Li2B oCllo may be effectively utilized because of their solubility in SO2 alone with concomitant current carrying capability.
Other fluid cathode depolarizers include thionyl chloride which is preferred in primary cell applications because of its high energy density ~3~;S~
and low vapor pressure. Other fluid cathode depolarizers generally util-izable in primary cell applications include f]uid oxyhalides3 non-metallic oxides and non-metallic halides and mixtures thereof such as phosphorous oxychloride (POCl3), selenium oxychloride (SeOC12), sulfur trioxide (S03) vanadium oxytrichloride (VOC13), chromyl chloride (CrO2Cl2), sulfuric oxy-chloride (S02C12), nitryl chloride (NOC12), nitrogen dioxide (N02), sulfur monochloride (S2C12) and sulfur monobromide (S2Br2). Each of the above can be used together with thionyl chloride (SOC12) or sulfur dioxide (S02) as fluid depolarizer/electrolyte solvent or separately.
The sulfur dioxide cathode depolarizer may be admixed with organic solvents such as acetonitrile, propylene carbonate and the llke to enhance solvation of salts in primary cell application. In such applications the more common electrolyte salts such as LiBr and the like may be utilized.
It may be noted that metal halides such as FeCl3 are soluble in SO
and metal halides such as CuC12 are soluble in organic solvents. However, with the intercalation of such metal halides with graphite they may be effectively utilized in cells containing sulfur dioxide alone or sulfur dioxide admixed with organic cosolvents.
The anode materials utilizable in the cells of the present inven-tion are active metals (i.e., above hydrogen in the EMF series) and include the alkali metals such as lithium (Li), sodium (Na) and potassium (K); the alkaline earth metals such as calcium (Ca) and magnesium (Mg), and aluminum (Al) and alloys of such metals particularly in the secondary cells of the present invention.
In constructing the cathodes of the present invention the graphite intercalated metal halides are generally admixed with small amounts, typically about 10%, of a binder such as polytetrafluoroethylene (PTFE) and then pasted onto a metal grid, such as of nickel, for support and as the cathode current collector.
~3~;54 In order to more fully illustrate the efficacy of the present inven-tion the following examples are presented. It is understood however that such examples are for illustrative purposes only and that specifics con-tained therein are not to be oonstrued as limitations on the present invention. Unless otherwise indicated all parts are parts by weight.
EXAMPLE 1 (PRIOR ART) A cell was made with a carbon cathode weighing 2.6 gms (90% Shawinigan black, 10% PTFE) pr~ssed in a 1.0" x 1.07" (2.5 x 2.7 cm) mold at 10,000 lb. on a ~li expanded metal grid to a thickness of 0.06". A nickel tab was attached thereto and the cathode was placed in a microporous polypropylene bag between two lithium-on-copper substrate layers within a prismatic cell.
The lithium capacity was 1.31 Ahr. The cell was then filled with lM
LiGaCl4 in S02 and placed on discharge at 6.6 mA (0.5 mA/cm ) and cycled between 2 and 3.8 volts. After about 20 cycles the cell failed because of cathod~ degradation and provlded a total of about 4 Ahrs.
EXAMPLE 2 (MODIFIED PRIOR ART) A cell was made as in Example 1 but with the electrodes having the dimensions 1.07" x 1.76" (2.7 x 4.5 cm) and the cathode being made oi graphite (Vulcan 72X, trademark of Cabot Corporation) and 10% PTFE. Though having a larger cathode, the cell failed almost immediately with a capacity oI only about 6 mAhrs.
A cell was made as in Example 1 but with a cathode comprised of graphite intercalated CoC12 (90% C and 10% CoC12) with lO~o PTFE binder.
The cell was placed on discharge at 6.6 mA (0.5 mA/cm ) and cycled between
This invention relates to primary and secondary non-aqueous fluid cathode depolarized cells particularly cells containing sulfur dioxide (S02) fluid cathode depolarizers.
Fluid cathode depolarized cells have generally contained inert carbon-aceous cathode or porous metals upon which the fluid cathode depolarizers are reduced during cell discharge. The porous metals were however somewhat unsatisfactory particularly at high rates because of their relatively low porosity when compared to the carbonaceous materials such as acetylene black and were therefore less preferred. The carbonaceous materials, while O satisfactory for primary cell application however suffered from degradation in secondary cells in which they were repeatedly expanded and contracted during the cell discharging and charging cycles respectively.
It is an object of the present invention to provide a fluld cathode depolarized cell with a catalytic cathode which is both highly porous and resistant to physical degradation.
It is a further object of the present invention to provide an effic-iently rechargeable S02 containing cell having such catalytic cathode.
These and other objects, features and advantages of the present inven-O tion will become more evident from the following discussion.
Generally the present invention comprises a non-aqueous fluid cathode depolarized cell with a catalytic cathode comprised of one or more graphite intercalated metal halides such as CuC12, CoC12, FeC13 and SbF5. Though graphite has generally been regarded as an unsuitable material for use as a cathode in fluid depolarized cells because of its tight lamellar structure, the graphite intercalated metal halides of the present invention have been found to be excellent porous cathode for fluid cathode depolarizer reduction in primary cell applications. Furthermore, cathodes made of the graphite intercalated metal halides of the present invention have been found to have a high degree of resiliency even under repeated expansion and contraction - during cycling in secondary cells. Thus the physical integrity of graphite 365~
intercalatedmetal halide cathodes is not seriously affected as compared to prior art carbonaceous cathodes generally used in rechargeable fluid cathode depolarized cells.
Some of the graphite intercalated~etal halides utilized in the cells of the present invention are, for example, commercially available under the Graphimet trademark (Alfa Division of Ventron Corp., Danvers, Mass.) and are generally 10 - 50% metal halide by weight. As opposed to simple mix-tures, the graphite intercalated metal halides are formed by reaction between the graphite and the metal halide whereby the lamellar structure of the graphite is opened to allow selective diffusion of molecules of proper spatial geometry therein. In the past, such graphite intercalated metal halides have been utilized as the actual active cathode materials of cells (U.S. patent no. 4.041,220 issued to Michel B. Armand). However, because of the very limited amount of reducible metal halide (50% or less) with such materials the capacity of such cells was very low. In contrast there-to the graphite intercalated metal halide cathode in the cell of the present invention i6 substantially inactive and serves as the catalytic site for the reduction of the high energy density fluid cathode depolari-zer.
The fluid cathode depolarizers utilized in the cell of the present invention include sulfur dioxide (SO2) which is utilizable in both primary and secondary cells. In secondary or rechargeable cells the sulfur dioxide is the sole electrolyte solvent since the further inclusion of organic cosolvents, as used in primary cells, reduces the cycling efficiencies with the production of generally irreversible reaction products. Thus, in the totally inorganic SO2 containing rechargeable cells only electrolytes such as gallium halide salts such as LiGaC14 or clovoborate salts such as Li2B oCllo may be effectively utilized because of their solubility in SO2 alone with concomitant current carrying capability.
Other fluid cathode depolarizers include thionyl chloride which is preferred in primary cell applications because of its high energy density ~3~;S~
and low vapor pressure. Other fluid cathode depolarizers generally util-izable in primary cell applications include f]uid oxyhalides3 non-metallic oxides and non-metallic halides and mixtures thereof such as phosphorous oxychloride (POCl3), selenium oxychloride (SeOC12), sulfur trioxide (S03) vanadium oxytrichloride (VOC13), chromyl chloride (CrO2Cl2), sulfuric oxy-chloride (S02C12), nitryl chloride (NOC12), nitrogen dioxide (N02), sulfur monochloride (S2C12) and sulfur monobromide (S2Br2). Each of the above can be used together with thionyl chloride (SOC12) or sulfur dioxide (S02) as fluid depolarizer/electrolyte solvent or separately.
The sulfur dioxide cathode depolarizer may be admixed with organic solvents such as acetonitrile, propylene carbonate and the llke to enhance solvation of salts in primary cell application. In such applications the more common electrolyte salts such as LiBr and the like may be utilized.
It may be noted that metal halides such as FeCl3 are soluble in SO
and metal halides such as CuC12 are soluble in organic solvents. However, with the intercalation of such metal halides with graphite they may be effectively utilized in cells containing sulfur dioxide alone or sulfur dioxide admixed with organic cosolvents.
The anode materials utilizable in the cells of the present inven-tion are active metals (i.e., above hydrogen in the EMF series) and include the alkali metals such as lithium (Li), sodium (Na) and potassium (K); the alkaline earth metals such as calcium (Ca) and magnesium (Mg), and aluminum (Al) and alloys of such metals particularly in the secondary cells of the present invention.
In constructing the cathodes of the present invention the graphite intercalated metal halides are generally admixed with small amounts, typically about 10%, of a binder such as polytetrafluoroethylene (PTFE) and then pasted onto a metal grid, such as of nickel, for support and as the cathode current collector.
~3~;54 In order to more fully illustrate the efficacy of the present inven-tion the following examples are presented. It is understood however that such examples are for illustrative purposes only and that specifics con-tained therein are not to be oonstrued as limitations on the present invention. Unless otherwise indicated all parts are parts by weight.
EXAMPLE 1 (PRIOR ART) A cell was made with a carbon cathode weighing 2.6 gms (90% Shawinigan black, 10% PTFE) pr~ssed in a 1.0" x 1.07" (2.5 x 2.7 cm) mold at 10,000 lb. on a ~li expanded metal grid to a thickness of 0.06". A nickel tab was attached thereto and the cathode was placed in a microporous polypropylene bag between two lithium-on-copper substrate layers within a prismatic cell.
The lithium capacity was 1.31 Ahr. The cell was then filled with lM
LiGaCl4 in S02 and placed on discharge at 6.6 mA (0.5 mA/cm ) and cycled between 2 and 3.8 volts. After about 20 cycles the cell failed because of cathod~ degradation and provlded a total of about 4 Ahrs.
EXAMPLE 2 (MODIFIED PRIOR ART) A cell was made as in Example 1 but with the electrodes having the dimensions 1.07" x 1.76" (2.7 x 4.5 cm) and the cathode being made oi graphite (Vulcan 72X, trademark of Cabot Corporation) and 10% PTFE. Though having a larger cathode, the cell failed almost immediately with a capacity oI only about 6 mAhrs.
A cell was made as in Example 1 but with a cathode comprised of graphite intercalated CoC12 (90% C and 10% CoC12) with lO~o PTFE binder.
The cell was placed on discharge at 6.6 mA (0.5 mA/cm ) and cycled between
2 and 3.~ volts. After the eighth cycle the discharge rate was increased to l3.3 mA (1.0 mA/cm ). The cell was cvcled 196 times with a total capacity of 15,6 Ahrs until the cell failed because of anode exhaustion.
**~Shawinigan Black is a trade maxk of Shawinigan Pr6ducts Corporation]
~3~
EXA~LE 4 A cell was made as in Example l but with a cathode comprlsed of graphite intercalated CuCl2 (90% C, 10~, CuCl2) with 10% PTFE binder. The cell was placed on discharge at 6.6 mA (0.5 mA/cm ) and cycled between 2.5 and 3.6 volts. After the third cycle the discharge rate was increased to 13.3 mA (1.0 mA/cm ). The cell was cycled 128 times with a total capacity of about 6.9 Ahrs when the cell failed because of a short circuit.
EXA~PLE 5 A cell was made as in Example 1 but with a cathode comprised of graphite intercalated FeC13 (85% C, 15% FeC13) with 10% PTFE binder. The cell was placed on discharge at 6.6 mA (0.5 mA/cm ) and cycled between 2 and 3.6 volts. The cell failed after 8 cycles because of a short circuit but delivered 3.4 Ahr.
A cell was made as in Example l but with a cathode comprised of graphite intercalated SbF5 (50% C, 50% SbF5) with 10% PTFE binder. The cell was placed on discharge at 6.6 mA (0.5 mA/cm ) and cycled between 2 and 3.6 volts. After 51 cycles and a cumulative capacity of 4.2 Ahr the cell cycling was stopped because of capacity loss.
The cells in Examples 3-6 all exhiblted discharge voltages attri-butable to S02 acting as the cathode depolarizer (i.e. about 2.8 volts).
Additionally the cells exhibited primary capacities during cycling well in excess of the theoretlcal metal halide capacities indicating that catalytic reduction of the S02 comprised the electrochemlcal reaction at the cathode.
It is understood that the above examples are illustrative in nature with the changes in cell structure, components and relative component ratios being possible without departing from the scope of the present invenion as defined in the following claims.
**~Shawinigan Black is a trade maxk of Shawinigan Pr6ducts Corporation]
~3~
EXA~LE 4 A cell was made as in Example l but with a cathode comprlsed of graphite intercalated CuCl2 (90% C, 10~, CuCl2) with 10% PTFE binder. The cell was placed on discharge at 6.6 mA (0.5 mA/cm ) and cycled between 2.5 and 3.6 volts. After the third cycle the discharge rate was increased to 13.3 mA (1.0 mA/cm ). The cell was cycled 128 times with a total capacity of about 6.9 Ahrs when the cell failed because of a short circuit.
EXA~PLE 5 A cell was made as in Example 1 but with a cathode comprised of graphite intercalated FeC13 (85% C, 15% FeC13) with 10% PTFE binder. The cell was placed on discharge at 6.6 mA (0.5 mA/cm ) and cycled between 2 and 3.6 volts. The cell failed after 8 cycles because of a short circuit but delivered 3.4 Ahr.
A cell was made as in Example l but with a cathode comprised of graphite intercalated SbF5 (50% C, 50% SbF5) with 10% PTFE binder. The cell was placed on discharge at 6.6 mA (0.5 mA/cm ) and cycled between 2 and 3.6 volts. After 51 cycles and a cumulative capacity of 4.2 Ahr the cell cycling was stopped because of capacity loss.
The cells in Examples 3-6 all exhiblted discharge voltages attri-butable to S02 acting as the cathode depolarizer (i.e. about 2.8 volts).
Additionally the cells exhibited primary capacities during cycling well in excess of the theoretlcal metal halide capacities indicating that catalytic reduction of the S02 comprised the electrochemlcal reaction at the cathode.
It is understood that the above examples are illustrative in nature with the changes in cell structure, components and relative component ratios being possible without departing from the scope of the present invenion as defined in the following claims.
Claims (9)
1. A non-aqueous electrochemical cell comprising an active metal anode, a fluid cathode depolarizer and a catalytic cathode comprised of at least one graphite intercalated metal halide.
2. The cell of claim 1 wherein said metal halide is selected from the group consisting of CoCl2, CuCl2, FeCl3 and SbF5.
3. The cell of claims 1 or 2 wherein said fluid cathode depolar-izer is selected from the group consisting of fluid oxyhalides, non metallic oxides, non metallic halides and mixtures thereof.
4. The cell of claim 2 wherein said active metal anode is com-prised of a member of the group consisting of Li, Na, K, Ca, Mg, and Al.
5. The cell of claim 4 wherein fluid cathode depolarizer is selected from the group consisting of SOCl2 and SO2.
6. The cell of claim 5 wherein said fluid cathode depolarizer is SO2.
7. A rechargeable inorganic non-aqueous electrochemical cell comprising a lithium anode, a fluid cathode depolarizer/electrolyte solvent consisting essentially of SO2, an electrolyte salt soluble in said SO2, and a catalytic cathode comprised of at least one graphite intercalated metal halide.
8. The cell of claim 7 wherein said metal halide is selected from the group consisting of CoCl2, CuCl2, FeCl3, and SbF5.
9. The cell of claims 7 or 8 wherein said electrolyte salt is selected from the group consisting of clovoborate and gallium halide salts.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000428679A CA1193654A (en) | 1983-05-24 | 1983-05-24 | Catalytic cathode for primary and secondary fluid cathode depolarized cells |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000428679A CA1193654A (en) | 1983-05-24 | 1983-05-24 | Catalytic cathode for primary and secondary fluid cathode depolarized cells |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1193654A true CA1193654A (en) | 1985-09-17 |
Family
ID=4125304
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000428679A Expired CA1193654A (en) | 1983-05-24 | 1983-05-24 | Catalytic cathode for primary and secondary fluid cathode depolarized cells |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1193654A (en) |
-
1983
- 1983-05-24 CA CA000428679A patent/CA1193654A/en not_active Expired
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