RECHARGEABLE MANGANESE OXIDE ELECTRODE MATERIALS

Abstract: Improved manganese oxide electrode materials are disclosed. The improved electrode materials may be cycled between discharged and charged states at higher utilization of reactant and for a substantially greater number of cycles than previously known manganese dioxide electrode mate­ rials. The improved manganese oxide electrode materials are characterized in that a heavy metal selected from the group consisting of bismuth, lead, and mixtures of bismuth and lead is included in the electrode material.

Description: RECHARGEABLE MANGANESE OXIDE ELECTRODE MATERIALS TECHNICAL FIELD This specification is directed to a development in rechargeable manganese oxide electrode materials. In particular, the development is one which results in a rechargeable manganese oxide electrode materials making such materials initially rechargeable up to about 90% of its theoretical two electron capacity. After 260 cycles, the electrode still retains above 50% of its theoretical two electron capacity. BACKGROUND ART AND PRIOR ART STATEMENT The manganese dioxide electrode has found wide application as a primary battery. One of the applications of such an electrode is in batteries used for a flashlight. The use of a flashlight is characteristic for an energy storage problem on a small scale; chemically stored energy is converted into electricity at will. We pay a high price for this conversion convenience. The throw-away battery may cost ten times the energy it stores simply to manufacture the battery. This is an important economic point of view considering that billions of these types of throw-away batteries are produced yearly throughout the world. It is already known that manganese dioxide cells of the alkaline version can be recharged a limited number of times so long as the cells are not discharged on their discharge cycle more than about 15% of their two electron capacity. Normally these cells can be recharged at this very reduced fraction of their two electron capacity only about 50 cycles or so. Thus, it is known that certain manganese dioxide cells of the alkaline version can be recharged for approximately 50 cycles or so if the reactant (manganese dioxide) utilization does not exceed about 15% of the two electron capacity. Rechargeable manganese oxide electrodes of our invention can be discharged a substantially greater amount than known cells in the discharge/recharge cycle and at the same time survive a significant number of cycles more than the presently known cells. With the improved rechargeable manganese oxide electrode material of our invention, we have built electrodes which can be initially discharged up to 90% of their total two electron capacity. We have been able to cycle such electrode containing cells in excess of 200 cycles between a discharged and recharged condition before their capacity dropped to about 50% of the theoretical two electron capacity. A search was conducted on the subject matter of this specification in the U.S. Patent and Trademark Office. As a result of that search, the following U.S. patents were cited as of interest: 3,066,179; 3,433,687; 3,615,833; 3,915,837; 4,009,052; 4,041,220; 4,049,887; 4,121,018; 4,125,687; and 4,286,589. After reviewing the patents, we were of the opinion that none of them disclosed the rechargeable manganese oxide electrode material which is to be disclosed in this specification. U.S. patent 4,286,589 did disclose an alkaline manganese dioxide cell which can be repeatedly recharged from a discharged state. This cell is made by chemically contacting the manganese dioxide with free liegatie ions of at least one weak acid that does not, in conditions prevailing in the cell, form salts with the manganese, the crystals of which contain water of crystallization. The patent disclosed that suitable weak acids were silicic, carbonic, boric, cyanic and acidic acids, and hydrogen sulfide. Although we are aware of what is going on in the development of rechargeable manganese oxide electrode materials, we are unaware of any prior art which is relevant to the improved manganese oxide electrode material of our invention. The utility and desirability of our improved manganese oxide electrode material is set forth in greater detail hereinbelow. DISCLOSURE OF THE INVENTION This invention relates to rechargeable manganese oxide electrode materials. Any one of the improved manganese oxide electrode materials is a material which can be cycled to greater discharge depths while being recharged from such discharge depths many times more than any previously known manganese oxide electrode material. In accordance with our invention, our improved manganese oxide electrode material is characterized in that a heavy metal selected from the group comprising bismuth, lead, and mixtures of bismuth and lead is included as an active element in the electrode material. The included bismuth, lead, and mixtures of bismuth and lead in the manganese oxide electrode material is "active" within our definition in that the presence of the heavy metal vastly improves rechargeability and improves the depth from which the electrode material can be recharged as well as the number of times that the electrode material may be recharged. These new manganese oxide electrode materials lead to practical and efficient rechargeable cells when the electrode material is coupled with another electrode material to form such a cell. We have found that the introduction of bismuth, lead, and mixtures of bismuth and lead into a manganese oxide electrode material vastly improves not only the depth of discharge from which the electrode material may be recharged, but also the number of times that the electrode material may be discharged and thereafter recharged while retaining high capacity. Substantial improvement of the reactant utilization as well as of the number of times the cell can be cycled comes about only when bismuth, lead, or mixtures of bismuth. and lead are included as an active element in the electrode material. Materials such as potassium, sodium, calcium, manganese, zinc, aluminum, and silver were tested and found not to be of any significant value in improving the rechargeability of a manganese oxide electrode material. According to a preferred, but not limiting, embodiment of the improved manganese oxide electrode materials of this invention, the materials are characterized in the following manner. Each of the improved manganese oxide electrode materials is characterized in that a heavy metal selected from the group consisting of bismuth, lead, and mixtures of bismuth and lead is included as an active element in the electrode material, the heavy metal initially being in a form not reacted with the manganese oxide electrode material which may consist, for example, of various forms of MnO2-or Birnessite. In essence, the improved manganese oxide electrode material is prepared by what we call a physical method" in which the heavy metal is mixed with the manganese oxide, but not chemically reacted therewith prior to utilization of the electrode material in a cell. In accordance with preferred teachings of this invention, each one of the improved manganese oxide electrode materials is characterized in that it is made in the following manner. A manganese oxide containing material is mixed with other electrode forming materials and with a metal compound in which the metal is a heavy metal selected from the group of heavy metals consisting of bismuth, lead, and mixtures of bismuth and lead. The electrode forming materials are formed into an electrode. The electrode is formed into a cell. After formation of the cell, the cell is electrically charged and discharged, for a few conditioning cycles. The cell so formed can be charged and recharged for a substantial percentage of its two electron capacity for a number of cycles substantially greater than previously known materials. BRIEF DESCRIPTION OF THE DRAWINGS The novel features that are considered characteristic of the invention are set forth with particularity in the appended claims. The invention itself, however, both as to its organization and its method of operation, together with additional objects and advantasges thereof, will best be understood from the following description and specific embodiments when read in connection with the accompanying drawings which are to graphs of the Percent of Utilization of a Reactant In a Non-Optimized Electrode as a Function of Cycle Number for various test materials set forth in the examples. BEST MODE AND INDUSTRIAL APPLICABILITY The following description is what we consider to be a preferred embodiment of our improved manganese oxide electrode materials. The following description also sets forth what we contemplate to be the best mode of carrying out the manufacture of the improved manganese oxide electrode materials in a physical method to form such improved manganese oxide electrode materials. This description of the preferred embodiment is not intended in any manner to be a limitation upon the broader principles of this improved electrode material. By a physical method, of course, we mean that the materials are simply mixed together to form the electrode, and no chemical reaction is intentionally carried out between the materials prior to their use in a cell. As stated above, we have found that if a manganese oxide electrode material is characterized in that a heavy metal selected from the group consisting of bismuth, lead, and mixtures of bismuth and lead is included as an active element therein, the manganese oxide electrode material has certain advantageous characteristics. These advantageous characteristics are that the number of cycles the electrode can undergo maintaining high reactant utilization is substantially greater than it was observed for any previously known manganese dioxide rechargeable electrode materials. Such advantages will be pointed in greater detail hereinbelow. In accordance with a preferred embodiment of this specification, a skilled artisan will be taught what we classify as a "physical method" for preparing the improved manganese oxide electrode materials in accordance with our invention. Our copending U.S. patent application Serial No. ¯¯¯¯¯¯¯¯¯¯¯, , filefiled on even date herewith-, sets forth what we classify as a "chemical method" for preparing a manganese dioxide electrode material which is in accordance with the teachings of that invention. The present application contains claims directed to the improved manganese oxide electrode materials prepared by the physical method. Examples 1. Bismuth Oxide-Manganese Dioxide Mixture This example will show the invention in the improved manganese oxide electrode material by illustrating a material in which bismuth is included as an active element in a manganese dioxide electrode material. The material illustrated is prepared by a physical method. 25 parts by weight of manganese dioxide (International Common Sample No. 1), after being ground for 18 hours in a pestle and mortar, was mixed with 10 parts by weight of Bi203 and 1800 parts by weight of graphite (SP-1) powder in a spex-mixer mill for approximately 10 minutes. The electrode paste was obtained by adding 1280 parts by weight of 9M KOH solution containing 4% by weight of an organic gelling agent to the dry powder and mixing for an additional five minutes. Electrodes were prepared from this material by sandwiching approximately 200 mg of the paste between two platinum gauze current collectors, themselves being sandwiched between two sheets of Celgard No. 3401 separators. The so-formed electrode (0.75" in diameter) was further wrapped in two additional sheets of Celgard No. 3401 separator and epoxyed on one side with Epoweld 3673 cement. The electrode was inserted into a 0.75" diameter (I.D.) Teflon tube, pressed at about 10 pounds per square inch pressure, and allowed to cure for 24 hours at room temperature. The so-produced electrode was cycled at 0.5 mV/sec in the range -0.6V to +0.2V (with respect to a Hg/HgO electrode). The results of this cycling of the test electrode are shown in Figure 1 as curve No. 1. This curve shows that during the initial cycling of the electrode, its percentage of utilization based on 2e actually increases. The curve also shows that when bismuth is used in the manganese dioxide electrode of material this Example 1, the improved material may be recycled a substantial number of times in excess of the 50 cycles and may be discharged in its highly cycled state to about 40% or more of its two electron capacity. This is substantially greater than any known rechargeable manganese dioxide electrode material which, for example, may be recycled at a maximum of only about 50 times at a discharge utilization of approximately 15% of its two electron capacity. 2. Lead Oxide-Manganese Dioxide Mixture This example will show the invention in the improved manganese oxide electrode material by illustrating a material in which lead is included as an active element in a manganese dioxide electrode material. The material illustrated is also prepared by a physical, method. Three grams of manganese dioxide (International Common Sample No. 1) were ground for 18 hours in a pestle and mortar and then were mixed with 1.07 grams of lead oxide and 210 grams of graphite for approximately 10 minutes. 1.02 grams of this mixture was then mixed with one gram of 9M KOH solution containing 4% by weight of an organic gelling agent in a spex-mixer mill for an additional five minutes. A modified manganese dioxide paste electrode was made using 0.208 grams of this mixture according to the procedure described in Example 1. Results of the cycling of this material are shown in Figure 1 as curve 2. While the testing ended at about 50 cycles for this compound, it can be seen that once again the percent utilization based on the two electron capacity initially increases during approximately the first 20 cycles or so until it reaches a maximum value, Once again, the percent utilization at the 50 cycle mark is significantly higher than that achieved by prior known materials. The increase in the percent of utilization would also be achieved at higher cycles, but the data was not obtained on this sample because we are familiar with the characteristics of the cell, and once it passes beyond 50 cycles with a capacity as significantly high as 30%, we are aware this is a desirable electrode material. 3. Bismuth Oxide-Manganese Dioxide Mixture This example will show the invention in the improved manganese oxide electrode material by illustrating a material in which bismuth is included as an active element in a manganese dioxide electrode material. The material illustrated is also prepared by a physical method. Five parts by weight of manganese dioxide (International Common Sample No. 1) was ground for 18 hours in a pestle and mortar and then mixed with two parts by weight of Bi2O3 and 165 parts by weight of graphite (SP-1) powder in a spex-mixer mill for approximately 10 minutes. A modified electrode paste was obtained by adding 300 parts by weight of 9M KOH solution containing 4% by weight of an organic gelling agent to the dry powder and mixing for an additional five minutes. A modified electrode was prepared by spreading 0.935 grams of the paste made in the manner described above in a 1" x 1" x 0.020" cavity of a 3" x 3" plexiglass sheet. The paste was covered with three layers of Celgard No. 3401 separator, which layers were in turn covered with a sheet of pellon paper which separated the improved manganese dioxide electrode from a NiO/NiOOH counterelectrode. This flat cell was cycled at 0.5 mV/sec in the range -0.6V to +0.2V (with respect to a Hg/HgO electrode) in a flat cell. Results of the cycling are shown in Figure 1 as curve 3. Once again, this curve demonstrated that during the initial cycling the percent utilization based on a two electron capacity increases to a maximum point. In this case, the maximum utilization approached 90+ percent. Once again, because of the excellent characteristics of this material, the testing thereof was terminated between 100 and 150 cycles. 4. Bismuth Oxide-Manganese Dioxide Mixture This example will show the invention in the improved manganese oxide electrode material by illustrating a material in which bismuth is included as an active element in a manganese dioxide electrode material. The material illustrated is also prepared by a physical method. The manganese dioxide used in this example, however, is a beta manganese dioxide which is a different form than the gamma manganese dioxide used in the first three examples. The same procedure as Examples 1-3 is followed, and the materials used are 100 mg of beta manganese dioxide (International Common Sample No. 6) with 42 mg of Bi203 and 6.9 grams of graphite powder. These materials, after being mixed, were in turn mixed with 8.8 grams of 9M KOH solution containing 4% by weight of an organic gelling agent. The material made in this manner was made into a device for testing in accordance with the procedure described in Example 1. Results of cycling of this electrode are shown in Figure 1 as curve 4. Once again, this curve has the characteristic of having its percent utilization based on its two electron capacity initially increase as the electrode material is cycled. 5. Bismuth Oxide-Manganese Dioxide Mixture This exam#ple will show the invention in the improved manganese oxide electrode material by illustrating material in which the bismuth is included as an active element in a manganese dioxide electrode material. The material illustrated is also prepared by a physical method. The type of manganese dioxide used, however, is a rho phase manganese dioxide. In this example, 8.8 parts by weight of rho/manganese dioxide (International Common Sample No. 7), after having been ground for 18 hours in a pestle and mor#tar, was mixed with three parts by weight of Bi203 and 540 parts by weight of graphite (SP-1) powder in a spex-mixer mill for approximately 10 minutes. To this mixture was added 705 parts by weight of 9H KOH solution containing 4% by weight of an organic gelling agent. This mixture was then mixed for an additional five minutes to obtain a paste. An electrode was made from the paste in the same manner as discussed in Example 1 and tested as per Example 1. The results of cycling are shown in Figure 1 as curve 5. 6. Bismuth Oxide-Manganese Dioxide Mixture This example will show the invention in the improved manganese oxide electrode material by illustrating a material in which the bismuth is included as an active element in a manganese dioxide electrode material. The material illustrated is also prepared by a physical method. 26 parts by weight of chemically prepared gamma manganese dioxide (International Common Sample No. 8), once having been ground for 18 hours in a pestle and mortar, was then mixed with 10 parts by weight of Bi203 and 1830 parts by weight of graphite (SP-1) powder for 10 minutes in a spex-mixer mill. A paste was obtained by adding 2325 parts by weight of 9M KOH solution containing 4% by weight of an organic gelling agent to the dry mixture and mixing for an additional five minutes. Electrodes were prepared using this paste mixture and tested in the same manner as set forth in Example 1. The results of the cycling are depicted in Figure 1 as curve 6. 7. Manganese Dioxide Alone The purpose of this example is to illustrate that when no heavy metal addition of the type described above is made to an International Common Sample No. 1 of manganese dioxide, the utilization and recharge capabilities of the cell of extremely poor. These procedure of Example 1 is carried out, except that there is no mixing Cf any elements with the manganese dioxide. Thus, test marq-nese di, je is used as described in the latter portion et Example 1 In order to manufacture an electrode which is s#-i:##'equently made into a cell. The manganese dioxide used was gamma manganese dioxide (International Common Sample No. 1). Testing of a cell produced using this material resulted in the data shown in Figure 1 as curve 7. This curve shows that the material can be cycled very little, and that very little cycling causes a disastrous loss in the utilization of the material based upon the percentage discharge one can obtain on the two electron capacity of this material. 8. Bismuth Oxide/Lead Oxide-Manganese Dioxide Mixture This example will show the invention in the improved manganese oxide electrode material by illustrating a material in which both bismuth and lead are included as an active element in a manganese dioxide electrode material. The material illustrated is also prepared by a physical method. 50.8 parts by weight of gamma manganese dioxide (International Common Sample No. 1), afte; being ground for 18 hours in a pestle and mortar, was mixed with five parts by weight of Mi203, 9. 26 parts by weight of PbO, and 3243 parts by weight of graphite (SP-l) powder in a spex-mixer mill for apEjroxímately two hours. A modified electrode paste was obtained by adding 3090 pasts by weight of 9M KOH solution containing 4% by weight of an organic binder to the dry powder and mixing for an additional one-half hour. Electrodes were prepared using this paste and tested according to the procedure described in Example 1. The resulting data is identified in Figure 1 as curve 8. 9. Birnessite Alone The purpose of this example is to illustrate that when no heavy metal addition of the type described above is made to a Birnessite sample, the utilization and recharge capabilities of the cell are extremely poor. The preparation of NaMnxOy compound is described in detail in our aforementioned copending application U.S. Serial No. ¯ , filed on even date herewith, which application is hereby incorporated by reference. In the process, Mn(OH)2 formed by a reaction of Mn(NO3)2 with excess NaOH at 0-30C was oxidized by 2 in a strong alkaline solution at 0-30C for five or more hours followed by filtering, thorough washing with water, and drying at 650C. Elemental analysis of the compound gave 48.8% Mn and 6.2% Na. NaMnxOy so formed was then ground and mixed with graphite powder of twice the weight. The mixture then was milled The mixture was then pressed at a pressure of 10 tons to form a disc of 1.2 cm diamter. A cell was formed using the so-formed disc as a cathode, platinum wjrp as an anode, and 9M KOH as an electrolyte. This cell was tested as constant current density of lma/0.02g of disc weight. The discharge/charge was cycled between running voltages of -0.5 to 0.5V against a HgO/Hg reference electrode. This cell used a Flex-Sil microporous rubber as the separator. The results of running this material are shown in Figure 2 as curve 1. This material, without any lead or bismuth additions, showed poor recharge capabilities. 10. Birnessite-Bismuth Oxide Mixture This example will show the invention in the improved manganese oxide electrode material by illustrating a material in which bismuth is included as an active element in a Birnessite material. The material illustrated is prepared by a physical method. The preparation of NaMnxoy compound has been described in Example 9. Weighed amounts of the so-formed material, along with Bi203 in a Mn:Bi mole ratio equal to 5.6, were mixed and ground in a mortar and pestle. Thereafter, the materials were mixed with graphite powder of twice the weight and milled. The mixture was pressed at a pressure of 10 tons to form a disc of 1.2 cm diameter. Cells were formed using these discs as a cathode, platinum wire as an anode, and 9M KOH as an electrolyte. The so-formed'cells were tested at constant current density of lma/O.02g of disc weight. The discharge/charge was cycled between running voltages of -0.5 to 0.5V against an HgO/Hg reference electrode. Flex-Sil microporous rubber was used as the separator. The results of the testing of the cell is shown in Figure 2 as curve 2. The curve shows that when bismuth is used in the Birnessite material, the improved material may be recycled a substantial number of times and may be discharged in its highly cycled state to a substantial proportion of its two electron capacity. 11. Birnessite-Bismuth Oxide Mixture This example will show the invention in the improved manganese oxide electrode material by illustrating a material in which bismuth is included as an active element in a Birnessite material. The material illustrated is prepared by a physical method. Birnessite was prepared as described in Example 9. 51 parts by weight of Birnessite that has been ground for 18 hours in a pestle and mortar was mixed with 14 parts by weight of Bi203 (Mn:Bi molar ratio equals 7) and 5013 parts by weight of graphite (SP-1) in a spex-mixer mill for approximately 10 minutes. 3083 parts by weight of 9M KOH solution containing 4% by weight of an organic gelling agent was added to this dry powder and mixed for an additional five minutes to obtain a paste. The electrode was made from this paste as discussed in Example 9 and tested for rechargeability in the manner described in Example 9. The resulting data is identified in Figure 2 as curve 3. 12. Birnessite-Lead Oxide Mixture This example will show the invention in the improved manganese oxide electrode material by illustrating a material in which lead is included as an active element in a Birnessite electrode material. The material illustrated is prepared by a physical method. The electrode is prepared as described in Example 10, except for Bi2O3 which was replaced by PbO in a Nm:Pb mole ratio of 4.2. The data resulting from testing of a cell having such an electrode contained therein is shown in Figure 2 as curve 4. 13. Birnessite-Bismuth Sulphide Mixture This example will show the invention in the improved manganese oxide electrode material by illustrating a material in which bismuth is included as an active element in a Birnessite electrode material. The material illustrated is prepared by a physical method. An electrode was prepared as described in Example 10, except that that Bi203 was replaced by Bi2S3 in a Mn:Bi molar ratio equal 10.8. The data obtained from testing of this electrode from into a cell is shown in Figure 2 as curve 5. General Factors to be Taken Into Account In order to make the improved manganese dioxide electrode material, it is necessary to include in that material fine powdered carbon or graphite to aid in the electronic conductivity of the material. An organic binder and/or gelling agent is also used in formation of the manganese dioxide electrode material. Normally, the organic gelling agent is made up of 4% by weight of carboxy methyl cellulose in 96% by weight of 9M KOH. It may be seen from the information reported above and the material presented graphically in the Figures that the inclusion of bismuth, lead, or mixtures of bismuth and lead in the manganese dioxide electrode brings about a rechargeability which is not seen in the manganese dioxide electrode by itself. This rechargeability enhancement is unique for the bismuth, lead, and bismuth/lead mixtures.

Claims: We claim: 1. An improved manganese oxide electrode material characterized in that a heavy metal selected from the group consisting of bismuth, lead, and mixtures of bismuth and lead is included as an active element in said electrode material. 2. An improved manganese oxide electrode material characterized in that a heavy metal selected from the group consisting of bismuth, lead, and mixtures of bismuth and lead is included as an active element in said electrode material, the heavy metal initially being in a form not reacted with the manganese dioxide. 3. The improved manganese oxide electrode of Claim 2, wherein said manganese oxide material is manganese dioxide. 4. The improved manganese oxide electrode of Claim 2, wherein said manganese oxide material is Birnessite. 5. An improved manganese dioxide electrode material characterized in that said material is made by: mixing a manganese oxide and other electrode forming materials with a metal salt in which the metal is a heavy metal selected from the group of heavy metals consisting of bismuth, lead, and mixtures of bismuth and lead; forming said electrode forming materials into an electrode; forming said electrode into a cell; and electrically charging and discharging said cell for a plurality of conditioning cycles. 6. The improved manganese oxide electrode of Claim 5, wherein said manganese oxide material is manganese dioxide. 7. The improved manganese oxide electrode of Claim 5, wherein said manganese oxide material is Birnessite.

Inventors: KUMMER, JOSEPH TALBOT, WROBLOWA, HALINA STEFANIA, YAO, YUNG-FANG
Applicants: FORD FRANCE SOCIETE ANONYME, FORD MOTOR COMPANY, FORD MOTOR COMPANY LIMITED, FORD-WERKE AKTIENGESELLSCHAFT
Application year: 1984
Main classification: H01M4
IPC codes: C01G45, H01M4, H01M10