GB2141285A - Catalytic cathode for primary and secondary fluid cathode depolarized cells - Google Patents
Catalytic cathode for primary and secondary fluid cathode depolarized cells Download PDFInfo
- Publication number
- GB2141285A GB2141285A GB08314536A GB8314536A GB2141285A GB 2141285 A GB2141285 A GB 2141285A GB 08314536 A GB08314536 A GB 08314536A GB 8314536 A GB8314536 A GB 8314536A GB 2141285 A GB2141285 A GB 2141285A
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- Prior art keywords
- cathode
- cell
- fluid
- group
- catalytic
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0563—Liquid materials, e.g. for Li-SOCl2 cells
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
-
- 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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
-
- 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
-
- 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
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
A fluid cathode depolarized cell having a catalytic cathode comprised of a graphite intercalated metal halide such as CuCl2, CoCl2, FeCl3 and SbF5.
Description
SPECIFICATION
Catalytic cathode for primary and secondary fluid cathode depolarized cells
This invention relates to primary and secondary non-aqueous fluid cathode depolarized cells particularly cells containing sulfur dioxide (SO2) fluid cathode depolarizers.
Fluid cathode depolarized cells have generally contained inert carbonaceous 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 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 fluid cathode depolarized cell with a catalytic cathode which is both highly porous and resistant to physical degradation.
It is a further object of the pres#ent invention to provide an efficiently rechargeable SO2 containing cell having such catalytic cathode.
These and other objects, features and advantages of the present invention will become more evident from the following discussion.
Generally the present invention comprises a nonaqueous fluid cathode depolarized cell with a catalytic cathode comprised of one or more intercalated metal halides such as CuC12, CoCI2, FeCI3 and SbFs.
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 intercalated metal 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 metal halides utilized in the cells of the present invention are, for example, commercially available underthe Graphimet trademark (Alfa Division of Ventron
Corp., Danvers, Mass.) and are generally 10 - 50% metal halide by weight. As opposed to simple mixtures, 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 thereto the graphite intercalated
metal halide cathode in the cell of the present
invention is substantially inactive and serves as the
catalytic site for the reduction of the high energy
density fluid cathode depolarizer.
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 contain
ing rechargeable cells only electrolytes such as
gallium halide salts such as LiGaCI4 or clovoborate
salts such as Li2B10C110 may be effectively utilized
because of their solubility in SO2 alone with concom
itant current carrying capability.
Other fluid cathode depolarizers include thionyl chloride which is preferred in primary cell applications because of its high energy density and low vapor pressure. Other fluid cathode depolarizers
generally utilizable in primary cell applications in
clude fluid oxyhalides, non-metallic oxides and
non-metallic halides and mixtures thereof such as
phosphorous oxychloride (POCI3), selenium oxych bride (SeOCI2), sulfurtrioxide (SO3) vanadium oxyt
richloride (VOCI3), chromyl chloride (CrO2Cl2), sulfur- ic oxychloride (SO2Cl2), nitryl chloride (NOCI2), nit
rogen dioxide (NO2), sulfur monochloride (S2CI2)
and sulfur monobromide (S2Br2).Each of the above
can be used together with thionyl chloride (SOCI2) or
sulfur dioxide (SO2) 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 like 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 FeCI3
are soluble in SO2 and metal halides such as CuCI2
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 invention are active metals (i.e., above
hydrogen in the EMF series) and include the alkali
metals such as lithium (Li), sodium (Na) and potas
sium (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 inven - tion the graphite intercalated metal halides are
generally admixed with small amounts, typically
about 10%, of a binder such as polytetraf
luoroethylene (PTFE) and then pasted onto a metal grid, such as of nickel, for support and as the cathode current collector.
In order to more fully illustrate the efficacy of the present invention the following examples are presented. It is understood however that such examples are for illustrative purposes only and that specifics contained therein are not to be construed as limitations on the present invention. Unless otherwise indicated all parts are parts by weight.
Example ? (prior art) A cell was made with a carbon cathode weighing 2.6 gms (90% Shawinigan black, 10% PTFE) pressed in a 1.0" x 1.07" (2.5 x 2.7 cm) mold at 10,000 lb. on a
Ni 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 ceil was then filled with 1 M LiGaCI4 in SO2 and placed on discharge at 6.6 mA (0.5 mA/cm2) and cycled between 2 and 3.8 volts. After about 20 cycles the cell failed because of cathode degradation and provided 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 of graphite (Vulcan 72X, trademark of Cabot Corporation) and 10% PTFE. Though having a larger cathode, the cell failed almost immediately with a capacity of only about 6 mAhrs.
Example 3 Acell was made as in Example 1 but with a cathode comprised of graphite intercalated CoCI2 (90% C and 10% Coy12) with 10% PTFE binder, The cell was placed on discharge at 6.6 mA (0.5 mA/cm2) and cycled between 2 and 3.8 volts. After the eighth cycle the discharge rate was increased to 13.3 mA (1.0 mA/cm2). The cell was cycled 196 times with a total capacity of 15.6 Ahrs until the cell failed because of anode exhaustion.
Example 4
A cell was made as in Example 1 but with a cathode comprised of graphite intercalated-CuCI2 (90% C, 10% Cut12) with 10% PTFE binder. The cell was placed on discharge at 6.6 mA (0.5 mA/cm2) 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/cm2). The cell was cycled 128 times with atotal capacity of about 6.9 Ahrs when the cell failed because of a short circuit.
Example 5
A cell was made as in Example 1-but with a cathode comprised of graphite intercalated FeCI3 (85% C, 15% FeCI3) with 10% PTFE binder. The cell was placed on discharge at 6.6 mA (0.5 mA/cm2) and cycled between 2 and 3.6 volts. The cell failed after 8 cycles because of a short circuit but delivered 3.4
Ahr.
Example 6
A cell was made as in Example 1 but with a cathode comprised of graphite intercalated SbFs (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 exhibited discharge voltages attributable to SO2 acting as the cathode depolarizer (i.e. about 2.8 volts). Additionally the cells exhibited primary capacities during cycling well in excess of the theoretical metal halide capacities indicating that catalytic reduction of the SO2 comprised the electrochemical 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 invention as defined in the following
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 CoCI2, Cut12, FeCI3 and SbF5.
3. The cell of claim 1 or 2 wherein said fluid cathode depolarizer is selected from the group consisting of fluid oxyhalides, non metallic oxides, non.metallic halides and mixtu#res thereof.
4. The cell of claim 2 wherein said active metal anode is comprised of a member of the group consisting of Li, Na, K, Ca, Mg, and Al.-
5. The cell of claim 4whereinfluid cathode depolarizer is selected from the group consisting of SOC12 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 m#e#tal halide.
8. The cell of claim 7 wherein said metal halide is selected from the group consisting of CoCI2, CuC12, FeCI3, 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 |
---|---|---|---|
GB08314536A GB2141285B (en) | 1983-05-26 | 1983-05-26 | Catalytic cathode for primary and secondary fluid cathode depolarized cells |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB08314536A GB2141285B (en) | 1983-05-26 | 1983-05-26 | Catalytic cathode for primary and secondary fluid cathode depolarized cells |
Publications (3)
Publication Number | Publication Date |
---|---|
GB8314536D0 GB8314536D0 (en) | 1983-06-29 |
GB2141285A true GB2141285A (en) | 1984-12-12 |
GB2141285B GB2141285B (en) | 1986-06-04 |
Family
ID=10543384
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB08314536A Expired GB2141285B (en) | 1983-05-26 | 1983-05-26 | Catalytic cathode for primary and secondary fluid cathode depolarized cells |
Country Status (1)
Country | Link |
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GB (1) | GB2141285B (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3917822A1 (en) * | 1988-06-06 | 1989-12-07 | Altus Corp | ELECTROCHEMICAL CELL AND METHOD FOR IMPROVING THE VOLTAGE SETTING THEREOF |
DE3918217A1 (en) * | 1988-08-29 | 1990-03-08 | Altus Corp | ELECTROCHEMICAL CELL AND METHOD FOR IMPROVING THE VOLTAGE SETTING OF THIS CELL |
DE3918168A1 (en) * | 1988-08-26 | 1990-03-08 | Altus Corp | RECHARGEABLE, NONWATER ELECTROCHEMICAL CELL |
-
1983
- 1983-05-26 GB GB08314536A patent/GB2141285B/en not_active Expired
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3917822A1 (en) * | 1988-06-06 | 1989-12-07 | Altus Corp | ELECTROCHEMICAL CELL AND METHOD FOR IMPROVING THE VOLTAGE SETTING THEREOF |
DE3918168A1 (en) * | 1988-08-26 | 1990-03-08 | Altus Corp | RECHARGEABLE, NONWATER ELECTROCHEMICAL CELL |
DE3918217A1 (en) * | 1988-08-29 | 1990-03-08 | Altus Corp | ELECTROCHEMICAL CELL AND METHOD FOR IMPROVING THE VOLTAGE SETTING OF THIS CELL |
Also Published As
Publication number | Publication date |
---|---|
GB2141285B (en) | 1986-06-04 |
GB8314536D0 (en) | 1983-06-29 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19930526 |