CA1186373A - Electrochemical cell with compacted cathode containing polyolefin powder additive - Google Patents
Electrochemical cell with compacted cathode containing polyolefin powder additiveInfo
- Publication number
- CA1186373A CA1186373A CA000422250A CA422250A CA1186373A CA 1186373 A CA1186373 A CA 1186373A CA 000422250 A CA000422250 A CA 000422250A CA 422250 A CA422250 A CA 422250A CA 1186373 A CA1186373 A CA 1186373A
- Authority
- CA
- Canada
- Prior art keywords
- cathode
- cell
- particulate
- extrusion
- polyolefin
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/06—Electrodes for primary cells
- H01M4/08—Processes of manufacture
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
Abstract
ELECTROCHEMICAL CELL WITH COMPACTED CATHODE
CONTAINING POLYOLEFIN POWDER ADDITIVE
ABSTRACT
An electrochemical cell having a compacted cathode wherein small amounts of a powdered polyolefin such a polypropylene are added to the active cathode material prior to compaction such as extrusion thereof.
CONTAINING POLYOLEFIN POWDER ADDITIVE
ABSTRACT
An electrochemical cell having a compacted cathode wherein small amounts of a powdered polyolefin such a polypropylene are added to the active cathode material prior to compaction such as extrusion thereof.
Description
3~73 This iDvention relates to electrochemical cells having compacted cathodes and more particularly to alkaline electrolyte cells having extruded cathodes.
Cathodes for cells su~h as alkaline electrolyte cells have been constructed by various compaction procedures whereby active materials such as mercuric oxide (BgO), silver oxide (Ag20) and manganese dioxide (MnO2) are pelletized or extruded into desired configurations. Cathode pellets are generally constructed under relatively high pressures (10,000 p5i or more) to form independent structures. In the extrusion procedure a cathode active mater$al together with conductive additives such as graphite or carbon and the cell electrolyte are admixed and plaeed in a cell container.
The mixture i5 then ex~ruded against the cell container walls by a punch at pressures of about 1200 psi. Sinee the extruded cathode is not structurally independent lower compactlng pressures are adequate.
In bo~h the pelletizing and extrusion procedures the cathode active n~tterials are admixed with graphite or carbon for both conductivity and for lubrication during ~he compacting. However, despite the presence of the graphite or carbon as a lubricant in relatively large amoun~s of generally about 6% or more of the cathode weight several problems have been encountered in the co~pacting procedures particularly with "wet" extrusions (compaction of a cathode mixture which includes fluid electrolyte). Additionally, cells m~de in accordance with such procedures have suffered from reduced dPlivered capaci~y because of such problems. The extruded cathodes tend to have large residual bottom thicknesses with such material being generally u~available for di~charge therefore resulting in reduced cell capacity.
FurthPrmore, desplte the presenc~ of the lubricaeing ~raphite or carbon, the cathodes do not have the entirely de6ired uniformity of density an~ as - a result cell efficiency is detrimentally affected.
It i~ an obje~t of the present invention to-provide a means wh~reby , . . .
the dischar~e ch~racter!stic6 of cell6 having eompactecl cathodes nre enhanced.
~36373 It is a further object of the present lnvention to provide such means whereby the procedure of cathDde compaction for said cells is also ~acilitated.
These and other objects, features and ad~antages of the present invention will become more evldent from the following discussion.
Generally, the present invention comprises an electrochemical cell having a compacted cathode wherein, prior to the compaction of the cathode such as by extrusion, a small amount of a finely powdered polyolefin such as polypropylene or polyethylene ~s added to the cathode ma~erials. It has been discovered that ~mall amounts of the powdered polyolefin, on the order of less than about 3% by weight of the cathode, unexpectedly m~rkedly improve the structure of the compacted cathode and the capacity o~ the cell containin~ such cathode. Additionally, particularly in the extrusion procedure, substantially reduced extrusion pressure (15% or more reduction) can be employed to Eorm the requlsite extruded cathode e.g. an extrusion pressure of about lOQ0 psi or less is sufficlent. Concomitantly, wear of the extrusion punch is also minimized.
The polyolefin powder additives, ~hich are useful in the practice of the present invention have particle sizes in the fini6hed cell ranging from about 30 microns to about 300 microns. Larger particle 6ized may, however, be initially added to the cathode mix prior to compaction provided that precompaction procedures (such as mixing with an intensifier bar) com-minutes the particles to ~he requisite dimenslons prior to the actual compaction (e.g. extrusion). The amount of the polyolefin powder added to the cathode should be minimal slnce it is non conductive and, unlike the conductive graphite or carbon, itB presence in larger amounts would impair conductlvity and capacity of the cathode. The amount of polyolefin powder added to the cathode materials prior to compaction i6 between about 0.1'~ to a maximum of about 3% by weight It iB preferred ~hat the amount of poly~-~lefin powder be present in an amount ranging from about n.2~ to ~bout 1%.
~ , IL18~i3'73 The polyolefin additives of the pre6ent invention are chemically stable and may be utilized with generally any powdered and compacted cathode material such as the aforementioned HgO, Ag20 and MnO2 active cathode ~aterials. Because of the ~tability of the polyolefin additives they may be utiliæed ln various cell environments such as alkaline cells having zlnc anodes and sodium or potassium hydroxide electrolyte solutions or non-aqueous electrolyte cells such as those having li~hium or other alkali or alkaline earth metal anodes.
In order to more fully illustrate the efficacy of the present invention the following examples are pre6ented. I~ is understood, however, that such examples are ~or illustrative purposes only and the invention is not limi~ed to specifics contained therein. ~nless otherwise indicated all parts are parts by weight.
Example 1 (PRIOR ART) A cathode mix comprised of 76% MnO2, 13.5% graphite (partlcle size of less than 10 microns), and 10.5% 7.2N KOH electrolyte solution was prepared and a 7.8 gram portiDn thereof was placed in a cell container (0.55" (1.4 cm) ID x 1.96" 5.0 cm) HT) and ex~ruded therein by a punch at 1200 psi against the cell container wall to form a cathode with an ID of O.366"
(0.93 cm). The cell was completed with the insertlon of a closed tubular separator into said cathode, the further insertion of about 3 grams of a gelled amalgamated zinc anode (93% Zn, 7% Hg) into the separ~tor and the addi~ion of about 2cc of 40% KOH electrolyte. After sealing of the cell ~t was discharged at a continuous discharge rate of 4 ohms with the results given in Table I.
Example 2 A cell was made in accordance with the procedure and with the materials in Example 1 b~t with 75.5% MnO2 and 0.5% powdered polypropylene (about 150 ~30 micron particle size). The cell was discharged as above with the results given in Table I.
~86373 TABLE I
Hour6 Hours VoltageExample 1 Cell Example 2 Cell % Improvement 1.10 l.58 1.77 12 1.00 2.82 2.9B 5.7 0.90 3.45 3.73 8.1 0.80 3.~9 4.38 1~.6 0.75 4.10 4.~0 12.2 Example 3 ~PRIOR ART) A cell ~as made as in Example 1 but from a cathode ~ix 74.5% MnO2, 14.5 % graphite (about 35 microns particle size) and 10.5% 7.2N KOH and discharged at a continuous rate of 4 ohms. The results are given in Table II.
Example 4 A cell was made as in Example 3 but with 74.5% MnO2 and 0.5~ powdered polypropylene ~about 150 micron particle size in the cathode mix). The cell was discharged as above and the results are given in Table II.
TABLE II
Hours Hours VoltageExample 3 Cell Example 4 Cell ~ Improvement 1.10 1.52 2.n5 34.9 1.00 2.6D 3.26 25.4 0.90 3.42 4.05 18.4 0.80 3.92 4.63 18.1 0.75 3.~2 4.78 21.9 : It is readily apparent from the above examples that despite the reduction of active cathode materials in the cathodes, the cells of Example.s 2 and 4 (havin~ the additive of the present invention) are markedly superior at all 363~3 cutoff voltages. It is further evident from Examples 3 and 4 that despite changes in amount and type of ~raphite and the reductlon cf active cathode material which causes reduction in capacity of ~he cell in Example 3, the ~capacity of the cell in Example 4 actually exhibits improved capacity.
It is understood that the above examples are for illustrative purposes only and that further changes in cell and cathode compositions and construc-tions may be made ~ithout departing from the scope of the present invention as defined in the following clai~s.
Cathodes for cells su~h as alkaline electrolyte cells have been constructed by various compaction procedures whereby active materials such as mercuric oxide (BgO), silver oxide (Ag20) and manganese dioxide (MnO2) are pelletized or extruded into desired configurations. Cathode pellets are generally constructed under relatively high pressures (10,000 p5i or more) to form independent structures. In the extrusion procedure a cathode active mater$al together with conductive additives such as graphite or carbon and the cell electrolyte are admixed and plaeed in a cell container.
The mixture i5 then ex~ruded against the cell container walls by a punch at pressures of about 1200 psi. Sinee the extruded cathode is not structurally independent lower compactlng pressures are adequate.
In bo~h the pelletizing and extrusion procedures the cathode active n~tterials are admixed with graphite or carbon for both conductivity and for lubrication during ~he compacting. However, despite the presence of the graphite or carbon as a lubricant in relatively large amoun~s of generally about 6% or more of the cathode weight several problems have been encountered in the co~pacting procedures particularly with "wet" extrusions (compaction of a cathode mixture which includes fluid electrolyte). Additionally, cells m~de in accordance with such procedures have suffered from reduced dPlivered capaci~y because of such problems. The extruded cathodes tend to have large residual bottom thicknesses with such material being generally u~available for di~charge therefore resulting in reduced cell capacity.
FurthPrmore, desplte the presenc~ of the lubricaeing ~raphite or carbon, the cathodes do not have the entirely de6ired uniformity of density an~ as - a result cell efficiency is detrimentally affected.
It i~ an obje~t of the present invention to-provide a means wh~reby , . . .
the dischar~e ch~racter!stic6 of cell6 having eompactecl cathodes nre enhanced.
~36373 It is a further object of the present lnvention to provide such means whereby the procedure of cathDde compaction for said cells is also ~acilitated.
These and other objects, features and ad~antages of the present invention will become more evldent from the following discussion.
Generally, the present invention comprises an electrochemical cell having a compacted cathode wherein, prior to the compaction of the cathode such as by extrusion, a small amount of a finely powdered polyolefin such as polypropylene or polyethylene ~s added to the cathode ma~erials. It has been discovered that ~mall amounts of the powdered polyolefin, on the order of less than about 3% by weight of the cathode, unexpectedly m~rkedly improve the structure of the compacted cathode and the capacity o~ the cell containin~ such cathode. Additionally, particularly in the extrusion procedure, substantially reduced extrusion pressure (15% or more reduction) can be employed to Eorm the requlsite extruded cathode e.g. an extrusion pressure of about lOQ0 psi or less is sufficlent. Concomitantly, wear of the extrusion punch is also minimized.
The polyolefin powder additives, ~hich are useful in the practice of the present invention have particle sizes in the fini6hed cell ranging from about 30 microns to about 300 microns. Larger particle 6ized may, however, be initially added to the cathode mix prior to compaction provided that precompaction procedures (such as mixing with an intensifier bar) com-minutes the particles to ~he requisite dimenslons prior to the actual compaction (e.g. extrusion). The amount of the polyolefin powder added to the cathode should be minimal slnce it is non conductive and, unlike the conductive graphite or carbon, itB presence in larger amounts would impair conductlvity and capacity of the cathode. The amount of polyolefin powder added to the cathode materials prior to compaction i6 between about 0.1'~ to a maximum of about 3% by weight It iB preferred ~hat the amount of poly~-~lefin powder be present in an amount ranging from about n.2~ to ~bout 1%.
~ , IL18~i3'73 The polyolefin additives of the pre6ent invention are chemically stable and may be utilized with generally any powdered and compacted cathode material such as the aforementioned HgO, Ag20 and MnO2 active cathode ~aterials. Because of the ~tability of the polyolefin additives they may be utiliæed ln various cell environments such as alkaline cells having zlnc anodes and sodium or potassium hydroxide electrolyte solutions or non-aqueous electrolyte cells such as those having li~hium or other alkali or alkaline earth metal anodes.
In order to more fully illustrate the efficacy of the present invention the following examples are pre6ented. I~ is understood, however, that such examples are ~or illustrative purposes only and the invention is not limi~ed to specifics contained therein. ~nless otherwise indicated all parts are parts by weight.
Example 1 (PRIOR ART) A cathode mix comprised of 76% MnO2, 13.5% graphite (partlcle size of less than 10 microns), and 10.5% 7.2N KOH electrolyte solution was prepared and a 7.8 gram portiDn thereof was placed in a cell container (0.55" (1.4 cm) ID x 1.96" 5.0 cm) HT) and ex~ruded therein by a punch at 1200 psi against the cell container wall to form a cathode with an ID of O.366"
(0.93 cm). The cell was completed with the insertlon of a closed tubular separator into said cathode, the further insertion of about 3 grams of a gelled amalgamated zinc anode (93% Zn, 7% Hg) into the separ~tor and the addi~ion of about 2cc of 40% KOH electrolyte. After sealing of the cell ~t was discharged at a continuous discharge rate of 4 ohms with the results given in Table I.
Example 2 A cell was made in accordance with the procedure and with the materials in Example 1 b~t with 75.5% MnO2 and 0.5% powdered polypropylene (about 150 ~30 micron particle size). The cell was discharged as above with the results given in Table I.
~86373 TABLE I
Hour6 Hours VoltageExample 1 Cell Example 2 Cell % Improvement 1.10 l.58 1.77 12 1.00 2.82 2.9B 5.7 0.90 3.45 3.73 8.1 0.80 3.~9 4.38 1~.6 0.75 4.10 4.~0 12.2 Example 3 ~PRIOR ART) A cell ~as made as in Example 1 but from a cathode ~ix 74.5% MnO2, 14.5 % graphite (about 35 microns particle size) and 10.5% 7.2N KOH and discharged at a continuous rate of 4 ohms. The results are given in Table II.
Example 4 A cell was made as in Example 3 but with 74.5% MnO2 and 0.5~ powdered polypropylene ~about 150 micron particle size in the cathode mix). The cell was discharged as above and the results are given in Table II.
TABLE II
Hours Hours VoltageExample 3 Cell Example 4 Cell ~ Improvement 1.10 1.52 2.n5 34.9 1.00 2.6D 3.26 25.4 0.90 3.42 4.05 18.4 0.80 3.92 4.63 18.1 0.75 3.~2 4.78 21.9 : It is readily apparent from the above examples that despite the reduction of active cathode materials in the cathodes, the cells of Example.s 2 and 4 (havin~ the additive of the present invention) are markedly superior at all 363~3 cutoff voltages. It is further evident from Examples 3 and 4 that despite changes in amount and type of ~raphite and the reductlon cf active cathode material which causes reduction in capacity of ~he cell in Example 3, the ~capacity of the cell in Example 4 actually exhibits improved capacity.
It is understood that the above examples are for illustrative purposes only and that further changes in cell and cathode compositions and construc-tions may be made ~ithout departing from the scope of the present invention as defined in the following clai~s.
Claims (15)
1. A cathode for an electrochemcial cell, comprising a compacted admixture of a particulate cathode active material, a particulate electron-ically conductive material, and from 0.1% to 3% by weight thereof of a particulate polyolefin material.
2. The cathode of claim 1 wherein said compaction comprises an extrusion of said cathode within a cell container.
3. The cathode of claim 2 wherein said cathode is formed by a wet extrusion.
4. The cathode of claim 2 wherein said polyolefin powder has a particle size ranging between 30 and 300 microns.
5. The cathode of claim 4 wherein said polyolefin powder comprises between 0.25% and 1% by weight of said cathode.
6. The cathode of claim 1 wherein said cathode active material is selected from the group consisting of HgO, Ag2O and MnO2.
7. The compacted cathode of claim 1 wherein said conductive material is selected from the group consisting of graphite and carbon.
8. A cell containing the cathode of claim 1, 4 or 5.
9. A cell containing a zinc anode, an alkaline electrolyte comprised of KOH and an extruded cathode comprised of MnO2, graphite and from 0.1% to 3% of a polypropylene powder having a particle size ranging between 30 and 300 microns.
10. A method for improving the compacting of a cathode for an elec-trochemical cell comprising the step of adding a particulate polyolefln to a cathode mixture comprising a particulate cathode active material and a particulate electronically conductive material prior to said compacting in an amount ranging between 0.1% to 3% of said cathode.
11. The method of claim 10 wherein said compacting comprises an extrusion of said cathode within a container of said cell.
12. The method of claim 11 wherein said extrusion is a wet extrusion.
13. The method of claim 10 wherein said polyolefin is selected from the group consisting of polyethylene and polypropylene.
14. The method of claim 13 wherein said conductive material is graphite.
15. The method of claim 14 wherein said polypropylene has a particle size ranging between 30 and 300 microns.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US36335382A | 1982-03-29 | 1982-03-29 | |
| US363,353 | 1982-03-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1186373A true CA1186373A (en) | 1985-04-30 |
Family
ID=23429877
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000422250A Expired CA1186373A (en) | 1982-03-29 | 1983-02-23 | Electrochemical cell with compacted cathode containing polyolefin powder additive |
Country Status (11)
| Country | Link |
|---|---|
| JP (1) | JPS58178959A (en) |
| AU (1) | AU554320B2 (en) |
| BE (1) | BE896052A (en) |
| BR (1) | BR8301564A (en) |
| CA (1) | CA1186373A (en) |
| DE (1) | DE3309833A1 (en) |
| ES (1) | ES520710A0 (en) |
| FR (1) | FR2524208A1 (en) |
| GB (1) | GB2118762B (en) |
| IT (1) | IT8320352A0 (en) |
| ZA (1) | ZA831265B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2568726B1 (en) * | 1984-05-14 | 1995-02-10 | Fuji Electrochemical Co Ltd | MANGANESE ALKALINE BATTERY |
| JP2925589B2 (en) * | 1989-08-11 | 1999-07-28 | 日立マクセル株式会社 | Alkaline manganese battery |
| KR940704069A (en) * | 1991-12-16 | 1994-12-12 | 글렌 워드러프 | COLLAPSING FOAM ANODE BACKING FOR ZINC-AIR BATTERY |
| US5458988A (en) * | 1993-08-10 | 1995-10-17 | Matsi, Inc. | Metal-air-cells having improved anode assemblies |
| DE19850474A1 (en) * | 1998-11-02 | 2000-05-04 | Varta Geraetebatterie Gmbh | Process for producing a positive electrode for an alkaline primary element |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2811572A (en) * | 1955-04-01 | 1957-10-29 | Fischbach Adolph | Method for making silver peroxide electrodes |
| DE1228685B (en) * | 1963-06-28 | 1966-11-17 | Varta Pertrix Union Ges Mit Be | Depolarizer mixture and process for its preparation |
| DE1771522A1 (en) * | 1968-06-04 | 1972-03-09 | Varta Ag | Silver oxide electrode for alkaline primary elements and process for their production |
| US3600231A (en) * | 1969-11-28 | 1971-08-17 | Esb Inc | Mercury cell |
| ZA732519B (en) * | 1972-07-03 | 1974-04-24 | Varta Batterie | Process for the manufacture of a positive electrode containing bonding agents for primary cells with alkaline electrolytes |
| JPS5333128B2 (en) * | 1973-10-31 | 1978-09-12 | ||
| FR2278171A1 (en) * | 1974-07-10 | 1976-02-06 | Tokyo Shibaura Electric Co | Positive electrode material for alkali-nickel oxide-zinc cell - contg manganese dioxide, improving capacity under high discharge load |
| JPS51142638A (en) * | 1975-06-03 | 1976-12-08 | Seiko Instr & Electronics | Silver peroxide battery |
| US4092464A (en) * | 1976-07-19 | 1978-05-30 | P. R. Mallory & Co. Inc. | Flexible cells and batteries formed therefrom |
| GB1537218A (en) * | 1976-09-07 | 1978-12-29 | Yardney Electric Corp | Binder for pressed nickel electrodes |
| JPS53126128A (en) * | 1977-04-08 | 1978-11-04 | Matsushita Electric Ind Co Ltd | Method of manufacturing electrode for lead storage battery |
| JPS53126129A (en) * | 1977-04-11 | 1978-11-04 | Matsushita Electric Ind Co Ltd | Method of manufacturing pasted electrode plate |
| US4078127A (en) * | 1977-04-21 | 1978-03-07 | Esb Incorporated | Additive for an alkaline battery employing divalent silver oxide positive active material |
| DE3069742D1 (en) * | 1979-06-26 | 1985-01-17 | Lucas Ind Plc | Zinc electrode for secondary electrochemical cells and electrochemical cells including said electrode |
| FR2466872B1 (en) * | 1979-10-02 | 1986-03-07 | Celsa Composants Electr Sa | LITHIUM BATTERY. MANGANESE BIOXIDE AND PROCESS FOR PRODUCING SUCH A BATTERY |
| FR2522881A1 (en) * | 1982-03-05 | 1983-09-09 | Seiko Instr & Electronics | BATTERY WITH SILVER OXIDE DIVALENT |
-
1983
- 1983-02-23 CA CA000422250A patent/CA1186373A/en not_active Expired
- 1983-02-24 ZA ZA831265A patent/ZA831265B/en unknown
- 1983-03-01 AU AU11927/83A patent/AU554320B2/en not_active Expired - Fee Related
- 1983-03-01 BE BE0/210232A patent/BE896052A/en not_active IP Right Cessation
- 1983-03-04 GB GB08305996A patent/GB2118762B/en not_active Expired
- 1983-03-08 FR FR8303753A patent/FR2524208A1/en not_active Withdrawn
- 1983-03-17 ES ES520710A patent/ES520710A0/en active Granted
- 1983-03-18 DE DE19833309833 patent/DE3309833A1/en not_active Withdrawn
- 1983-03-25 BR BR8301564A patent/BR8301564A/en unknown
- 1983-03-28 JP JP58052312A patent/JPS58178959A/en active Pending
- 1983-03-29 IT IT8320352A patent/IT8320352A0/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| AU554320B2 (en) | 1986-08-14 |
| ES8403668A1 (en) | 1984-03-16 |
| ES520710A0 (en) | 1984-03-16 |
| DE3309833A1 (en) | 1983-10-06 |
| JPS58178959A (en) | 1983-10-20 |
| BR8301564A (en) | 1983-12-06 |
| GB8305996D0 (en) | 1983-04-07 |
| FR2524208A1 (en) | 1983-09-30 |
| GB2118762A (en) | 1983-11-02 |
| ZA831265B (en) | 1983-11-30 |
| BE896052A (en) | 1983-07-01 |
| GB2118762B (en) | 1985-04-11 |
| IT8320352A0 (en) | 1983-03-29 |
| AU1192783A (en) | 1983-10-06 |
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Legal Events
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| MKEX | Expiry |