CA2178423A1 - Cathodes for electrochemical cells having additives - Google Patents
Cathodes for electrochemical cells having additivesInfo
- Publication number
- CA2178423A1 CA2178423A1 CA002178423A CA2178423A CA2178423A1 CA 2178423 A1 CA2178423 A1 CA 2178423A1 CA 002178423 A CA002178423 A CA 002178423A CA 2178423 A CA2178423 A CA 2178423A CA 2178423 A1 CA2178423 A1 CA 2178423A1
- Authority
- CA
- Canada
- Prior art keywords
- cathode
- cell
- additive
- electrochemical cell
- 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.)
- Abandoned
Links
- 239000000654 additive Substances 0.000 title claims abstract description 55
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 43
- 230000000996 additive effect Effects 0.000 claims abstract description 37
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003792 electrolyte Substances 0.000 claims abstract description 13
- 239000011149 active material Substances 0.000 claims abstract description 12
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims abstract description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011701 zinc Substances 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 abstract description 14
- 229910002113 barium titanate Inorganic materials 0.000 abstract description 4
- -1 K2TiO3 Inorganic materials 0.000 abstract description 2
- 229910000831 Steel Inorganic materials 0.000 description 18
- 239000010959 steel Substances 0.000 description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920001778 nylon Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910001369 Brass Inorganic materials 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- 239000010951 brass Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002985 plastic film Substances 0.000 description 3
- 229920006255 plastic film Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910019096 CoTiO3 Inorganic materials 0.000 description 2
- 229910002370 SrTiO3 Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(II) oxide Inorganic materials [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten(VI) oxide Inorganic materials O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 229910010252 TiO3 Inorganic materials 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000012866 crystallographic experiment Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical class C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 101150016746 sigI gene Proteins 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
-
- 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
-
- 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
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
- H01M2300/0014—Alkaline electrolytes
-
- 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
- H01M6/04—Cells with aqueous electrolyte
Abstract
A cathode for use in an electrochemical cell having an anode and an electrolyte.The cathode includes a manganese dioxide active material and an additive which includes at least one of SnO2, Fe2O3-TiO2, TiO2 (P-25), BaTiO3, K2TiO3, Nb2O5, or SnO. The cathode of the present invention is particularly adapted for use in anelectrochemical cell having a zinc anode and an alkaline electrolyte.
Description
2178~Z3 .
PATENT APPLICATION
Atty. Docket No. EVE01 P471 CATHODES FOR ELECTROCHEMICAL CELLS HAVING ADDITIVES
BACKGROUND OF THE INVENTION
The present invention generally relates to electrochemical cells including cathode additives and more particularly to primary ~lk~linP electrochemical cells having cathodes formed of m~ng~nPse dioxide, one or more oxide additives, and other cathode components.
S Typical ~Ik~linP cells include a steel cylindrical can having a cathode Co~ g m~n~arlPse dioxide as the active material and formed on the interior surface of the steel can, an anode comrising zinc and located in the center of the cell, a separator film located between the anode and the cathode, and an alkaline electrolyte simultaneously contacting the anode, cathode, and separator. A conductive anode current collector is inserted into the anode active material and a seal assemb~y closes the open end of the steel can.
A primary goal in designing ~Ik~line batteries is to increase the service performance of the cell. The service performance is the length of time for the cell to discharge under a given load to a specific voltage at which the cell is no longer useful for its intende-l purpose. One approach taken to increase service performance was to increase the interior vloume of the cell in order to increase the amount of active materials within the cell. However, the commercial external siæ of the cell is fixed, thereby limiting the ability to increase the amounts of active materials within the cell.
In order to accommodate more active materials within the cell while m~int~ining the external siæ of the cell, the steel label of the col,~/enlional alkaline cell has been replaced with one made of thinner mPt~li7Pd plastic film. Thus, the steel can may be enlarged to provide a greater internal volume. By switching to a thinner plastic film label, the service performance of a typical ~Ik~linP cell was significantly increased.
Another approach taken to increase the service performance of a cell is to provide for better utilization of the electrodes' materials. This approach is taken in 21~8~23 U.S. Patent No. 5,342,712 issued to Mieczkowska et al., which discloses lltili7.ing an anatase tit~nillm dioxide as an additive to a cathode having m~ng~n~se dioxide as the active material. Despite past i~ ases in service pelrol,llal1ce, the need to find new ways to increase service performance remains the primary goal of cell designers.
S SUMMARY OF THE INVENTION
The present invention improves the service pelr~ lance of ~Ik~lin~ cells by the addition of one or more oxide additives to the active cathode material. To achieve this and other advantages, and in accol~lance with the purpose of the invention as embodied and broadly described herein, the cathode of the present invention comprises a m~ng~n~se dioxide active material and an additive, which colll~lises one or more of SnO2, Fe,03-TiO2, ~l02 (P-25), BarlO3, K~TiO3, Nb205, Al2O3, WO3, CoTiO3, SrTiO3, SnO, or V2O5. The cathode of the present invention is particularly adapted for use in an electrochemical cell having a zinc anode and an ~Ik~lin~
electrolyte.
These and other features, objects, and benefits of the invention will be recognized by those who practice the invention and by those skilled in the art, from reading the following specification and claims together with reference to the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 is a cutaway perspective view of an example of an electrochemical cell constructed in accordance with the present invention;
Fig. 2 is a comparative graph of the service performance of a standard ~Ik~linP
cell having a cathode with no additives and electrochemical cells having cathodes with additives in accordance with the present invention;
Fig. 3 is a comparative graph of the service performance of a standard ~Ik~linl cell having a cathode with no additives and electrochemical cells having cathodes with additives in accordance with the present invention;
217~23 Fig. 4 is a comparative graph of the service performance of a standard ~Ik~linP
cell having a cathode with no additives and an electrochemical cell having a cathode with an additive in accordance witn the present invention; and Fig. S is a comparative graph of the service perfornance of a standard ~Ik~lin~
S cell having a cathode with no additives and an electrochemical cell having a cathode with an additive in accordance with the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Fig. 1 shows a cutaway view of a typical cylindrical ~lk~lin~o battery l0.
Alkaline battery 10 includes a steel can 15 having a cylindrical shape and one open end. A met~li7~cl, plastic film label 16 is formed about the exterior surface of steel can 15 except for t'ne ends of steel can 15. At the closed end of steel can 15 is a positive cover 17 preferably formed of plated steel. Film label 16 is formed over the peripheral edge of positive cover 17.
A cathode 20 preferably formed of a mixture of m~ng~n~se dioxide, graphite, 45% potassium hydroxide solution, deioni_ed water, a TEFLONn' solution, and an-additive, is formed about the interior side surface of steel can 15. A separator 30, which is preferably formed of a non-woven fabric that prevents migration of any solid particles in the battery, is disposed about the interior surface of cathode 20. An electrolyte 40 formed of potassium hydroxide is disposed in the interior of separator 30. An anode 50, preferably formed of zinc powder, a gelling agent and other additives, is disposed within electrolyte 40 in contact with a current collector 60, which may be formed of brass.
Current collector 60 contacts a brass rivet 70 formed at the open end of steel can 15. A nylon seal 71 is formed at the open end of steel can 15 to prevent leakage of the active ingredients contained in steel can 15. Nylon seal 71 contacts a metal washer 72 and an inner cell cover 74, which is preferably formed of steel. A
negative cover 75, which is preferably formed of plated steel is disposed in contact with inner cell cover 74 and brass rivet 70, which contacts current collector 60 through a hole formed in nylon seal 71. Negative cover 75 is electrically inc~ ted from steel can 15 by nylon seal 71.
The cathode of the present invention for a D-siæ cell is preferably composed of app~ ;".~tely 71.76 to 81.66 weight percent ~nO2, about 8.52 weight percent graphite, about 7.87 weight percent ~Ik~linP solution, such as a 45% KOH solution, about 0.36 weight percent deionized water, about 1.49 weight percent binder material, such as a TEFLONn' solution, and app~ ly 0.1 to 10 weight percent of an additive. More preferably, the weight percent of MnO2 is between about 76.76 and80.76 and the weight percent of the additive is between 1 and 5 such that the combined weight percent of MnO2 and the additive is a constant of preferably ~pplo~illlately 81.76. The amount of ~Ik~line solution used in the cathode varies according to cell size as does the amount of the binder material. Preferably, the additive is SnO2, but may also include SnO, BaTiO3, K.Ti03, Al,03, Fe~O3-FlO., TiO2 (P-25), W03, SrTi03, CoTi03, Nb205, or V20s. TiO~ (P-25) is a fumed tit~nillm dioxide available from Degussa Corporation. Unlike most forms of titanium dioxide, which are produced using a precipitation technique, TiO2 (P-25) is produced by high telllpeldture (> 1200C) flame hydrolysis of TiCl4 in the presence of O. and H,. From the burner, a coagulation of primary particles takes place during cooling which results in the final particle size and distribution. A series of cyclones separate the solid material from reaction gases. The product is then subjected to steam to remove HCI which is a by-product from the reaction. rlo2 (P-25) is non-porous and has a particle shape that is cubic in nature with rounded edges. Crystallographic study of rlo2 (P-25) shows that multiphases of amorphous, anatase and rutile forms exist. The anatase-to-rutile ratio is between 70:30 and 80:20.
The cathode can be made by weighing out the needed materials and mixing the MnO2, the additive, and the graphite and blending to obtain a homogeneous mixture.
Then, the deionized water, the TEFLONn' solution and the KOH solution are mixed with the dry cathode components to form a homogeneous cathode mix. The cathode mixture is then placed in steel can 15 and molded into an ~nmll~r, cylindrical shape.
217~ i2~
-As stated above, it has been discovered that the addition of small amounts of the above listed additives significantly increases the service performance of ~Ik~lin~
electrochemical cells. The following comparative examples illustrate the advantages obtained from practicing the present invention.
A control ~lk~lin~ D-size cell was prepared as described above except no additive was included in the cathode and the weight percentage attributed to theadditive was provided by additional MnO2. A first ~I,elilllental D-siæ cell having a cathode with 1.6 weight percent SnO2, a second experimental D-size cell having an additive of Fe2O3-TiO2, and a third experimental D-size cell including a TiO2 (P-25) additive were also constructed. The four cells were continuously conn~cte~ to a 1.0 Ohm load and the voltages of the cells were measured over a period of time. Fig. 2 shows a graph of the time versus voltage discharge profiles of the four cells. At a cutoff voltage of 0.75 volt, the first experimental cell including the SnO2 additive exhibited a 24% increase in service pelrollllance over the control cell. The second experimental cell including the Fe2O3-TiO2 additive, and the third experimental cell-including the TiO2 (P-25) additive had a 9% increase in service perforrnance over the control cell.
A fourth experiment~l D-size cell having a BaTi03 additive and a fifth experimental D-size cell having a K2TiO3 additive were constructed, along with acontrol cell having no additive. The three cells were cormected to a 2.2 Ohm load for one hour per day. Fig. 3 shows the resulting time versus voltage discharge profiles for the three cells. For a 1.00 volt cutoff, the fifth experirnental cell with the K2TiO3 additive showed a 10% increase over the service pelrollllance of the control cell and the fourth experimental cell having the BaTiO3 additive exhibited an 8% increase in service pelrullllance over the control cell. At a 0.80 volt cutoff, the fifth experimental cell having the K2TiO3 additive had a 13% increase in service performance over the control cell, while the fourth experimental cell had a 10%
increase in service perforrnance over the control cell.
217~;? 3 A sixth cA~e,ullental D-size cell having a Nb205 additive and a control cell having no additive were constructed and subjected to a 2.2 Ohm light interrnittent fl~hlight (LIF) test, whereby the cells were connected to a 2.2 Ohm load for four mimltes per hour for eight collseculi~e hours per day. Fig. 4 shows the resulting time versus voltage dischar;ge profiles for the sixth ~A~e~ullental cell and the control cell.
At a 1.00 volt cutoff, the sixth experimental cell showed no improvement in service performance over the control cell. However, at a 0.90 volt cutoff, the sixth experimental cell had a 7% increase in service performance over the control cell.
A control ~Ik~lin~ AA-size cell was prepared as described above using the same weight percentages as used for the control D-size cell except no additive was included in tne cathode and the weight percentage attributed to the additive wasprovided by additional MnO,. A seventh experimental AA-size cell having a cathode with 1.6 weight percent SnO2 and an eighth experimental AA-size cell having an additive of TiO2 additive were also constructed. The three cells were subjected to an IEC photoflash test by conn~cting the cells to a 1.8 Ohm load for cycles of fifteen seconds ON and forty-five seconds OFF (i.e., each cycle equalling one minute) and the voltages of the cells were measured over a period of ON/OFF cycles. Fig. 5 shows a graph of the cycle versus voltage discharge profiles of the three cells. At a cutoff voltage of 0.9 volt, the seventh experimental cell including the SnO. additive exhibited a 25 % illclease in service performance over the control cell. The eighth ~;p~ lental cell including the TiO2 additive had a 15% increase in service performance over the control cell. As apparent from the above comparative examples, sigI~ificant increases in service performance of an ~Ik~line electrochemical cell may be obtained using additives of SnO2, Fe203-TiO2, Ti02 (P-25), Ba~l037 K2TiO3, and Nb2O5. Increases in service performance have also been obtained using additives of SnO, Al2O3, W03, SrTiO3, CoTiO3, and V2O5.
Although the above comparative examples were restricted to D and AA-size cells, it will be ap~r~ciat~d by those skilled in the art that the increase in service 217~ i23 performance may be obtained regardless of the size of the cell. Because some of the above additives perform better than others in continuous tests while others perform better in intermittent tests, it is desirable to combine such additives to enh~nre the overall service performance of an electrochemical ceil for both continuous and intermittent use.
It will be understood by those who practice the invention and by those skilled in the art, that various modirlcations and hllylo~e~llents may be made to the invention without departing from the spirit of the disclosed concept. The scope of protection afforded is to be determined by the claims and by the breadth of i~telL~lct~Lionallowed by law.
PATENT APPLICATION
Atty. Docket No. EVE01 P471 CATHODES FOR ELECTROCHEMICAL CELLS HAVING ADDITIVES
BACKGROUND OF THE INVENTION
The present invention generally relates to electrochemical cells including cathode additives and more particularly to primary ~lk~linP electrochemical cells having cathodes formed of m~ng~nPse dioxide, one or more oxide additives, and other cathode components.
S Typical ~Ik~linP cells include a steel cylindrical can having a cathode Co~ g m~n~arlPse dioxide as the active material and formed on the interior surface of the steel can, an anode comrising zinc and located in the center of the cell, a separator film located between the anode and the cathode, and an alkaline electrolyte simultaneously contacting the anode, cathode, and separator. A conductive anode current collector is inserted into the anode active material and a seal assemb~y closes the open end of the steel can.
A primary goal in designing ~Ik~line batteries is to increase the service performance of the cell. The service performance is the length of time for the cell to discharge under a given load to a specific voltage at which the cell is no longer useful for its intende-l purpose. One approach taken to increase service performance was to increase the interior vloume of the cell in order to increase the amount of active materials within the cell. However, the commercial external siæ of the cell is fixed, thereby limiting the ability to increase the amounts of active materials within the cell.
In order to accommodate more active materials within the cell while m~int~ining the external siæ of the cell, the steel label of the col,~/enlional alkaline cell has been replaced with one made of thinner mPt~li7Pd plastic film. Thus, the steel can may be enlarged to provide a greater internal volume. By switching to a thinner plastic film label, the service performance of a typical ~Ik~linP cell was significantly increased.
Another approach taken to increase the service performance of a cell is to provide for better utilization of the electrodes' materials. This approach is taken in 21~8~23 U.S. Patent No. 5,342,712 issued to Mieczkowska et al., which discloses lltili7.ing an anatase tit~nillm dioxide as an additive to a cathode having m~ng~n~se dioxide as the active material. Despite past i~ ases in service pelrol,llal1ce, the need to find new ways to increase service performance remains the primary goal of cell designers.
S SUMMARY OF THE INVENTION
The present invention improves the service pelr~ lance of ~Ik~lin~ cells by the addition of one or more oxide additives to the active cathode material. To achieve this and other advantages, and in accol~lance with the purpose of the invention as embodied and broadly described herein, the cathode of the present invention comprises a m~ng~n~se dioxide active material and an additive, which colll~lises one or more of SnO2, Fe,03-TiO2, ~l02 (P-25), BarlO3, K~TiO3, Nb205, Al2O3, WO3, CoTiO3, SrTiO3, SnO, or V2O5. The cathode of the present invention is particularly adapted for use in an electrochemical cell having a zinc anode and an ~Ik~lin~
electrolyte.
These and other features, objects, and benefits of the invention will be recognized by those who practice the invention and by those skilled in the art, from reading the following specification and claims together with reference to the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 is a cutaway perspective view of an example of an electrochemical cell constructed in accordance with the present invention;
Fig. 2 is a comparative graph of the service performance of a standard ~Ik~linP
cell having a cathode with no additives and electrochemical cells having cathodes with additives in accordance with the present invention;
Fig. 3 is a comparative graph of the service performance of a standard ~Ik~linl cell having a cathode with no additives and electrochemical cells having cathodes with additives in accordance with the present invention;
217~23 Fig. 4 is a comparative graph of the service performance of a standard ~Ik~linP
cell having a cathode with no additives and an electrochemical cell having a cathode with an additive in accordance witn the present invention; and Fig. S is a comparative graph of the service perfornance of a standard ~Ik~lin~
S cell having a cathode with no additives and an electrochemical cell having a cathode with an additive in accordance with the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Fig. 1 shows a cutaway view of a typical cylindrical ~lk~lin~o battery l0.
Alkaline battery 10 includes a steel can 15 having a cylindrical shape and one open end. A met~li7~cl, plastic film label 16 is formed about the exterior surface of steel can 15 except for t'ne ends of steel can 15. At the closed end of steel can 15 is a positive cover 17 preferably formed of plated steel. Film label 16 is formed over the peripheral edge of positive cover 17.
A cathode 20 preferably formed of a mixture of m~ng~n~se dioxide, graphite, 45% potassium hydroxide solution, deioni_ed water, a TEFLONn' solution, and an-additive, is formed about the interior side surface of steel can 15. A separator 30, which is preferably formed of a non-woven fabric that prevents migration of any solid particles in the battery, is disposed about the interior surface of cathode 20. An electrolyte 40 formed of potassium hydroxide is disposed in the interior of separator 30. An anode 50, preferably formed of zinc powder, a gelling agent and other additives, is disposed within electrolyte 40 in contact with a current collector 60, which may be formed of brass.
Current collector 60 contacts a brass rivet 70 formed at the open end of steel can 15. A nylon seal 71 is formed at the open end of steel can 15 to prevent leakage of the active ingredients contained in steel can 15. Nylon seal 71 contacts a metal washer 72 and an inner cell cover 74, which is preferably formed of steel. A
negative cover 75, which is preferably formed of plated steel is disposed in contact with inner cell cover 74 and brass rivet 70, which contacts current collector 60 through a hole formed in nylon seal 71. Negative cover 75 is electrically inc~ ted from steel can 15 by nylon seal 71.
The cathode of the present invention for a D-siæ cell is preferably composed of app~ ;".~tely 71.76 to 81.66 weight percent ~nO2, about 8.52 weight percent graphite, about 7.87 weight percent ~Ik~linP solution, such as a 45% KOH solution, about 0.36 weight percent deionized water, about 1.49 weight percent binder material, such as a TEFLONn' solution, and app~ ly 0.1 to 10 weight percent of an additive. More preferably, the weight percent of MnO2 is between about 76.76 and80.76 and the weight percent of the additive is between 1 and 5 such that the combined weight percent of MnO2 and the additive is a constant of preferably ~pplo~illlately 81.76. The amount of ~Ik~line solution used in the cathode varies according to cell size as does the amount of the binder material. Preferably, the additive is SnO2, but may also include SnO, BaTiO3, K.Ti03, Al,03, Fe~O3-FlO., TiO2 (P-25), W03, SrTi03, CoTi03, Nb205, or V20s. TiO~ (P-25) is a fumed tit~nillm dioxide available from Degussa Corporation. Unlike most forms of titanium dioxide, which are produced using a precipitation technique, TiO2 (P-25) is produced by high telllpeldture (> 1200C) flame hydrolysis of TiCl4 in the presence of O. and H,. From the burner, a coagulation of primary particles takes place during cooling which results in the final particle size and distribution. A series of cyclones separate the solid material from reaction gases. The product is then subjected to steam to remove HCI which is a by-product from the reaction. rlo2 (P-25) is non-porous and has a particle shape that is cubic in nature with rounded edges. Crystallographic study of rlo2 (P-25) shows that multiphases of amorphous, anatase and rutile forms exist. The anatase-to-rutile ratio is between 70:30 and 80:20.
The cathode can be made by weighing out the needed materials and mixing the MnO2, the additive, and the graphite and blending to obtain a homogeneous mixture.
Then, the deionized water, the TEFLONn' solution and the KOH solution are mixed with the dry cathode components to form a homogeneous cathode mix. The cathode mixture is then placed in steel can 15 and molded into an ~nmll~r, cylindrical shape.
217~ i2~
-As stated above, it has been discovered that the addition of small amounts of the above listed additives significantly increases the service performance of ~Ik~lin~
electrochemical cells. The following comparative examples illustrate the advantages obtained from practicing the present invention.
A control ~lk~lin~ D-size cell was prepared as described above except no additive was included in the cathode and the weight percentage attributed to theadditive was provided by additional MnO2. A first ~I,elilllental D-siæ cell having a cathode with 1.6 weight percent SnO2, a second experimental D-size cell having an additive of Fe2O3-TiO2, and a third experimental D-size cell including a TiO2 (P-25) additive were also constructed. The four cells were continuously conn~cte~ to a 1.0 Ohm load and the voltages of the cells were measured over a period of time. Fig. 2 shows a graph of the time versus voltage discharge profiles of the four cells. At a cutoff voltage of 0.75 volt, the first experimental cell including the SnO2 additive exhibited a 24% increase in service pelrollllance over the control cell. The second experimental cell including the Fe2O3-TiO2 additive, and the third experimental cell-including the TiO2 (P-25) additive had a 9% increase in service perforrnance over the control cell.
A fourth experiment~l D-size cell having a BaTi03 additive and a fifth experimental D-size cell having a K2TiO3 additive were constructed, along with acontrol cell having no additive. The three cells were cormected to a 2.2 Ohm load for one hour per day. Fig. 3 shows the resulting time versus voltage discharge profiles for the three cells. For a 1.00 volt cutoff, the fifth experirnental cell with the K2TiO3 additive showed a 10% increase over the service pelrollllance of the control cell and the fourth experimental cell having the BaTiO3 additive exhibited an 8% increase in service pelrullllance over the control cell. At a 0.80 volt cutoff, the fifth experimental cell having the K2TiO3 additive had a 13% increase in service performance over the control cell, while the fourth experimental cell had a 10%
increase in service perforrnance over the control cell.
217~;? 3 A sixth cA~e,ullental D-size cell having a Nb205 additive and a control cell having no additive were constructed and subjected to a 2.2 Ohm light interrnittent fl~hlight (LIF) test, whereby the cells were connected to a 2.2 Ohm load for four mimltes per hour for eight collseculi~e hours per day. Fig. 4 shows the resulting time versus voltage dischar;ge profiles for the sixth ~A~e~ullental cell and the control cell.
At a 1.00 volt cutoff, the sixth experimental cell showed no improvement in service performance over the control cell. However, at a 0.90 volt cutoff, the sixth experimental cell had a 7% increase in service performance over the control cell.
A control ~Ik~lin~ AA-size cell was prepared as described above using the same weight percentages as used for the control D-size cell except no additive was included in tne cathode and the weight percentage attributed to the additive wasprovided by additional MnO,. A seventh experimental AA-size cell having a cathode with 1.6 weight percent SnO2 and an eighth experimental AA-size cell having an additive of TiO2 additive were also constructed. The three cells were subjected to an IEC photoflash test by conn~cting the cells to a 1.8 Ohm load for cycles of fifteen seconds ON and forty-five seconds OFF (i.e., each cycle equalling one minute) and the voltages of the cells were measured over a period of ON/OFF cycles. Fig. 5 shows a graph of the cycle versus voltage discharge profiles of the three cells. At a cutoff voltage of 0.9 volt, the seventh experimental cell including the SnO. additive exhibited a 25 % illclease in service performance over the control cell. The eighth ~;p~ lental cell including the TiO2 additive had a 15% increase in service performance over the control cell. As apparent from the above comparative examples, sigI~ificant increases in service performance of an ~Ik~line electrochemical cell may be obtained using additives of SnO2, Fe203-TiO2, Ti02 (P-25), Ba~l037 K2TiO3, and Nb2O5. Increases in service performance have also been obtained using additives of SnO, Al2O3, W03, SrTiO3, CoTiO3, and V2O5.
Although the above comparative examples were restricted to D and AA-size cells, it will be ap~r~ciat~d by those skilled in the art that the increase in service 217~ i23 performance may be obtained regardless of the size of the cell. Because some of the above additives perform better than others in continuous tests while others perform better in intermittent tests, it is desirable to combine such additives to enh~nre the overall service performance of an electrochemical ceil for both continuous and intermittent use.
It will be understood by those who practice the invention and by those skilled in the art, that various modirlcations and hllylo~e~llents may be made to the invention without departing from the spirit of the disclosed concept. The scope of protection afforded is to be determined by the claims and by the breadth of i~telL~lct~Lionallowed by law.
Claims (9)
1. An electrochemical cell having an anode, a cathode, and an electrolyte, said cathode comprising a manganese dioxide active material and an additive comprising Fe2O3-TiO2.
2. The electrochemical cell as defined in claim 1, wherein said anode includes zinc and the electrolyte is an alkaline electrolyte.
3. The electrochemical cell as defined in claim 1, wherein said additive constitutes between about 0.1 to 10 weight percent of said cathode.
4. An electrochemical cell having an anode, a cathode, and an electrolyte, said cathode comprising a manganese dioxide active material and an additive comprising fumed TiO2.
5. An electrochemical cell having an anode, a cathode, and an electrolyte, said cathode comprising a manganese dioxide active material and an additive comprising a combination of anatase and rutile TiO2.
6. The electrochemical cell as defined in claim 5, wherein said combination of anatase and rutile TiO2 includes at least 20 percent rutile TiO2.
7. An electrochemical cell having an anode, a cathode, and an electrolyte, said cathode comprising a manganese dioxide active material and an additive comprising Nb2O5.
8. The electrochemical cell as defined in claim 7, wherein said additive constitutes between about 0.1 to 10 weight percent of said cathode.
9. An electrochemical cell having an anode, a cathode, and an electrolyte, said cathode comprising a manganese dioxide active material and an additive comprising SnO.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/485,424 | 1995-06-07 | ||
| US08/485,424 US5599644A (en) | 1995-06-07 | 1995-06-07 | Cathodes for electrochemical cells having additives |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2178423A1 true CA2178423A1 (en) | 1996-12-08 |
Family
ID=23928117
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002178423A Abandoned CA2178423A1 (en) | 1995-06-07 | 1996-06-06 | Cathodes for electrochemical cells having additives |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US5599644A (en) |
| EP (1) | EP0747982B1 (en) |
| JP (1) | JP4015716B2 (en) |
| KR (1) | KR970000136A (en) |
| CN (1) | CN1147703A (en) |
| CA (1) | CA2178423A1 (en) |
| DE (1) | DE69606352T2 (en) |
| HK (1) | HK1007408A1 (en) |
| SG (1) | SG68585A1 (en) |
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- 1995-06-07 US US08/485,424 patent/US5599644A/en not_active Expired - Lifetime
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- 1996-06-06 CA CA002178423A patent/CA2178423A1/en not_active Abandoned
- 1996-06-06 JP JP14393096A patent/JP4015716B2/en not_active Expired - Lifetime
- 1996-06-07 EP EP96304263A patent/EP0747982B1/en not_active Expired - Lifetime
- 1996-06-07 DE DE69606352T patent/DE69606352T2/en not_active Expired - Lifetime
- 1996-06-07 CN CN96106837A patent/CN1147703A/en active Pending
- 1996-06-07 KR KR1019960020274A patent/KR970000136A/en not_active Application Discontinuation
- 1996-06-07 SG SG1996010009A patent/SG68585A1/en unknown
-
1998
- 1998-06-24 HK HK98106312A patent/HK1007408A1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| EP0747982A1 (en) | 1996-12-11 |
| DE69606352D1 (en) | 2000-03-02 |
| EP0747982B1 (en) | 2000-01-26 |
| SG68585A1 (en) | 1999-11-16 |
| JPH09106811A (en) | 1997-04-22 |
| US5599644A (en) | 1997-02-04 |
| HK1007408A1 (en) | 1999-04-09 |
| KR970000136A (en) | 1997-01-21 |
| DE69606352T2 (en) | 2000-08-24 |
| JP4015716B2 (en) | 2007-11-28 |
| CN1147703A (en) | 1997-04-16 |
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