US2655456A - Manganese dioxide for primary cells - Google Patents

Manganese dioxide for primary cells Download PDF

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US2655456A
US2655456A US213949A US21394951A US2655456A US 2655456 A US2655456 A US 2655456A US 213949 A US213949 A US 213949A US 21394951 A US21394951 A US 21394951A US 2655456 A US2655456 A US 2655456A
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manganese dioxide
inch
meshes
weight
particles
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US213949A
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Gullett William Waitman
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Manganese Battery Corp
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Manganese Battery Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • This invention relates to the improvement of manganese dioxide for primary cells. It relates particularly to the improvement of bulk density of otherwise satisfactory battery oxide. It has forits aim the improvement of the bulk density of synthetic manganese dioxide without adversely afiecting its depolarizing properties.
  • synthetic manganese dioxide such as that made by oxidizing manganese carbonate has good depolarizing properties but has a lower bulk density than natural African ore or battery oxide prepared by the electrolytic process.
  • the bulk density of synthetic chemicaloxide variesfrom about 9-12 grams per cubic inch while natural electrolytic ore varies from 18-22 grams per cubic inch.
  • FIG. 1 there are illustrated typical discharge curves of Le Clanche cells.
  • curve A corresponds to a, cell made with a synthetic oxide
  • curve B to an identical cell made with the same synthetic oxide densified in accordance with my invention.
  • comparative discharge curves are shown for identical alkaline cells.
  • Curve 3 in this figure shows the discharge of a cell made With synthetic oxide, and curve A, the'discharge of a cell made afterdensification of this oxide by the practice of my invention. Details of the construction of the cells of these illustrations will be found in Examples 1 and 3 respectively.
  • I takesynthetic chemical manganese dioxide and mix it withgraphite. I then press themixture at atemperature of 450-650 F and a pressure of 10-50 tons per square inch. I then take the pellet so formed and crush it so that the product will pass a standard screen with 60 meshes to the linear inch and remain at least in substantial proportion on a standard screen with 200 meshes to the linear inch.
  • the bulk density of such a product will be from -23 grams per cubic inch and will show on test in a Le Clanche cell an improvement in initial capacity. approximately proportional to the increase in bulk density.
  • composite graphite-manganese-di oxide particles produced by comminutionis also critical. particles sized to pass a standard screen having.
  • the crystal structure as determined by X-ray analysis was the so-called gamma. This material had a bulk density when measured on Scott volumeter of 12 grams per cubic inch. This material when made into Size AA Le Clanche cells showed a discharge through 300 ohms which has been plotted as curve a, Figure 1.
  • 70% of the material would pass a screen with 100 meshes to the linear inch but not one with 125 meshes.
  • 20% of the material would pass a screen with 125 meshes to the linear inch but not one with 150 meshes.
  • This material showed a bulk density of 22.1
  • Example 2 I take manganese dioxide such as is commercially available as a by-product of saccharin manufacture. This material is of high purity and is substantially amorphous. The apparent bulk density of this product is 7-8 grams per cubic inch. This material is mixed with 10% by weight of micronized natural graphite and pressed at 500 F. and tons per square inch.
  • the resulting pellets are comminuted so that the.
  • Example 3 I take oxide like that used in Example 1 and mix with 15% by weight of Acheson artificial graphite powder. I press this material at 600 F. and 40 tons per square inch. The resulting pellets are comminuted so that all of the composite particles will pass a screen with 60 meshes to the linear inch but not one with 100 meshes. The bulk density of this product was 15 grams per cubic inch. The product is made into a depolarizer for an alkaline cell by mixing with 2% by weight of powdered natural graphite and cold-pressing into a A diameter steel can at 40 tons per square inch. The electrolyte used was 30% KOH and the anode a compressed pellet of granular amalgamated zinc. This cell was discharged through a constant resistance of 300 ohms.
  • a discharge curve for such a cell is shown in curve a, of Figure 2.
  • curve b Figure 2
  • the method of producing composite particles of chemical synthetic manganese dioxide and graphite having a bulk density of 1523 grams per cubic inch which includes the steps of mixing chemical synthetic manganese dioxide with 1-15% by weight graphite powder, pressing the mixture at a temperature between 400 F. and 650 F. and a pressure of 10-50 tons per square inch, cooling the pellet so formed, and comminuting it so that the resulting particles will all pass a standard screen having 60 meshes to the linear inch and at least by weight of the particles will remain on a screen having 200 meshes to the linear inch.
  • the method of improving the bulk density of synthetic manganese dioxide without impairing its depolarizing properties which includes the steps of mixing chemical synthetic manganese dioxide with 1-5% by weight graphite powder, pressing the mixture at a temperature between 400 F. and 650 F. at a pressure of 10-50 tons per square inch, cooling the pellet so formed and comminuting it so that the resulting particles will all pass a standard screen having 60 meshes to the linear inch and at least 80% by weight of the particles will be larger in average diameter than the original manganese dioxide.
  • the method of making a depolarizer for primary cells which includes the steps of mixing synthetic manganese dioxide having a gamma structure with 1-5% powdered graphite, heating to 400-600 F., pressing the mixture while at this temperature at 10-40 tons per square inch, then comminuting the resultant pellet to obtain particles which will all pass a standard screen having at least 60 meshes to the linear inch.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Description

Patented Oct. 13, 1953 MAN GANE SEDIOXIDE FOR IRIMARY CELLS William Waitman Gullett, College Park, Md., as: signer. to Manganese Battery Corporation, Riverdale, Md., avcorporation Application March 5, 1951, Serial No. 213,949.
3 Claims.
This invention relates to the improvement of manganese dioxide for primary cells. It relates particularly to the improvement of bulk density of otherwise satisfactory battery oxide. It has forits aim the improvement of the bulk density of synthetic manganese dioxide without adversely afiecting its depolarizing properties.
It is Well known in the art that synthetic manganese dioxide such as that made by oxidizing manganese carbonate has good depolarizing properties but has a lower bulk density than natural African ore or battery oxide prepared by the electrolytic process. For example, the bulk density of synthetic chemicaloxide variesfrom about 9-12 grams per cubic inch while natural electrolytic ore varies from 18-22 grams per cubic inch.
In this application the term bulk density will be used to designate the grams per cubic inch of the oxide as determined by the Scott volumeter.
The initial capacity'of Le Clanche cells made from synthetic chemical oxide is less than that of cells made from electrolytic oxide substantially in proportion to the lower apparent density.
I have found that if chemical synthetic oxides be densified in accordance with my invention'that the initial capacity of Le Clanche cells made with them, is increased in proportion to, the density increase.
In Figure 1 there are illustrated typical discharge curves of Le Clanche cells. Inthi figure, curve A corresponds to a, cell made with a synthetic oxide, and curve B, to an identical cell made with the same synthetic oxide densified in accordance with my invention. InFigure 2, comparative discharge curves are shown for identical alkaline cells. Curve 3 in this figure shows the discharge of a cell made With synthetic oxide, and curve A, the'discharge of a cell made afterdensification of this oxide by the practice of my invention. Details of the construction of the cells of these illustrations will be found in Examples 1 and 3 respectively.
In carrying. out the process of this invention I takesynthetic chemical manganese dioxide and mix it withgraphite. I then press themixture at atemperature of 450-650 F and a pressure of 10-50 tons per square inch. I then take the pellet so formed and crush it so that the product will pass a standard screen with 60 meshes to the linear inch and remain at least in substantial proportion on a standard screen with 200 meshes to the linear inch. The bulk density of such a product will be from -23 grams per cubic inch and will show on test in a Le Clanche cell an improvement in initial capacity. approximately proportional to the increase in bulk density.
I have found that the temperature and pressure of compacting the graphitemanganese. dioxide mixture is critical. Even at the optimum temperature of 600 F. there is substantially no improvement with pressures below 10 tons per: square inch. The maximum improvementinthe range 450-650" F. is obtained at approximately tons per square inch and at pressures above tons per square inch there is a rapid falling off of the improvement in density.
There is substantially no improvement below 450 F. regardless of pressure and a rapid d'eterioration above 650 F. The maximum improve-- rnent is obtained at about 600 F. at all pressures within the range 10-50 tons per square inch. The amount of graphite is also critical.
graphite- Smaller amounts down to 1% by.
weight give limited improvement and there is.
little or no improvement in density above 1.5% by weight of. graphite.
The size of composite graphite-manganese-di oxide particles produced by comminutionisalso critical. particles sized to pass a standard screen having.
80 meshe to thelinear inch and remain on.- one. Particles intermediate in;
having. 100 meshes. size between those which all remain on a.- screen having meshes to the linear inch and those-of such size that by weight will remain on a.
Having now described the general principles; or my invention, I will illustrateit by specific ex-- amples.
Example I I take synthetic manganese dioxide made by the oxidation of fully crystalline manganese carbonate and leaching with 10% sulphuric acid. This manganese dioxide has an analysis as follows:
Available oxygen as per cent MnOz 89.1 Iotal manganese as per cent Mn 58.5 Moisture as per cent H2O 1.9 Iron as per cent Fe 0.3 Silica as per cent SiOz Nil pH 4.1
The. best results are obtained with by. weight of.
The maximum density is obtained with,
The crystal structure as determined by X-ray analysis was the so-called gamma. This material had a bulk density when measured on Scott volumeter of 12 grams per cubic inch. This material when made into Size AA Le Clanche cells showed a discharge through 300 ohms which has been plotted as curve a, Figure 1.
The same manganese dioxide was mixed with by weight micronized graphite and hotpressed at 600 F. and 40 tons per square inch. The pressure was applied only instantaneously. The pellet produced in this way was cooled and comminuted to the following sieve analysis:
70% of the material would pass a screen with 100 meshes to the linear inch but not one with 125 meshes.
20% of the material would pass a screen with 125 meshes to the linear inch but not one with 150 meshes.
7% of the material would pass a screen with 150 meshes to the linear inch but not one with 200 meshes.
3% passed through a screen with 200 meshes to the linear inch.
This material showed a bulk density of 22.1
grams per cubic inch when tested in the Scott volumeter.
This material was then made into identical Le Clanche cells and subjected to the same test as the unpressed manganese dioxide. The discharge curve is shown in curve I) of Figure 1.
The improvement of density and performance of the oxide treated in accordance with my invention is clear.
Example 2 I take manganese dioxide such as is commercially available as a by-product of saccharin manufacture. This material is of high purity and is substantially amorphous. The apparent bulk density of this product is 7-8 grams per cubic inch. This material is mixed with 10% by weight of micronized natural graphite and pressed at 500 F. and tons per square inch.
The resulting pellets are comminuted so that the.
Example 3 I take oxide like that used in Example 1 and mix with 15% by weight of Acheson artificial graphite powder. I press this material at 600 F. and 40 tons per square inch. The resulting pellets are comminuted so that all of the composite particles will pass a screen with 60 meshes to the linear inch but not one with 100 meshes. The bulk density of this product was 15 grams per cubic inch. The product is made into a depolarizer for an alkaline cell by mixing with 2% by weight of powdered natural graphite and cold-pressing into a A diameter steel can at 40 tons per square inch. The electrolyte used was 30% KOH and the anode a compressed pellet of granular amalgamated zinc. This cell was discharged through a constant resistance of 300 ohms. A discharge curve for such a cell is shown in curve a, of Figure 2. In curve b, Figure 2, is shown the discharge curve of an identical cell made with the oxide as mixed with 15% Acheson artificial graphite powder and coldpressed into the diameter steel can at 40 tons per square inch. This cell was also discharged through a constant resistance of 300 ohms.
What is claimed is:
1. The method of producing composite particles of chemical synthetic manganese dioxide and graphite having a bulk density of 1523 grams per cubic inch which includes the steps of mixing chemical synthetic manganese dioxide with 1-15% by weight graphite powder, pressing the mixture at a temperature between 400 F. and 650 F. and a pressure of 10-50 tons per square inch, cooling the pellet so formed, and comminuting it so that the resulting particles will all pass a standard screen having 60 meshes to the linear inch and at least by weight of the particles will remain on a screen having 200 meshes to the linear inch.
2. The method of improving the bulk density of synthetic manganese dioxide without impairing its depolarizing properties which includes the steps of mixing chemical synthetic manganese dioxide with 1-5% by weight graphite powder, pressing the mixture at a temperature between 400 F. and 650 F. at a pressure of 10-50 tons per square inch, cooling the pellet so formed and comminuting it so that the resulting particles will all pass a standard screen having 60 meshes to the linear inch and at least 80% by weight of the particles will be larger in average diameter than the original manganese dioxide.
3. The method of making a depolarizer for primary cells which includes the steps of mixing synthetic manganese dioxide having a gamma structure with 1-5% powdered graphite, heating to 400-600 F., pressing the mixture while at this temperature at 10-40 tons per square inch, then comminuting the resultant pellet to obtain particles which will all pass a standard screen having at least 60 meshes to the linear inch.
WILLIAM WAITMAN GULLETT.
References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 642,414 Bachmann et a1. Jan. 30, 1900 1,272,406 Ellis July 16, 1918 1,293,272 Wells Feb. 4, 1919 1,296,700 Ruhofi Mar. 11, 1919 1,637,433 Yngve Aug. 2, 1927 1,724,886 Peiler Aug. 13, 1929 2,091,569 Ridgway et a1 Aug. 31, 1937 2,208,185 Goudge May 27, 1939 2,307,301 Hileman Jan. 5, 1943

Claims (1)

1. THE METHOD OF PRODUCING COMPOSITE PARTICLES OF CHEMICAL SYNTHETIC MANGANESE DIOXIDE AND GRAPHITE HAVING A BULK DENSITY OF 15-23 GRAMS PER CUBIC INCH WHICH INCLUDES THE STEPS OF MIXING CHEMICAL SYNTHETIC MANGANESE DIOXIDE WITH 1-515% BY WEIGHT GRAPHITE POWDER, PRESSING THE MIXTURE AT A TEMPERATURE BETWEEN 400* F. AND 650* F. AND A PRESSURE OF 10-50 TONS PER SQUARE INCH, COOLING THE PELLET SO FORMED, AND COMMINUTING IT SO THAT THE RESULTING PARTICLES WILL ALL PASS A STANDARD SCREEN HAVING 60 MESHES TO THE LINEAR INCH AND AT LEAST 80% BY WEIGHT OF THE PARTICLES WILL REMAIN ON A SCREEN HAVING 200 MESHES TO THE LINEAR INCH.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2739914A (en) * 1954-05-19 1956-03-27 Manganese Chemicals Corp Manganese dioxide depolarizer
FR2356283A1 (en) * 1976-06-23 1978-01-20 Niggl Hans SHIELDING PLATE, FOR ACCUMULATOR

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US642414A (en) * 1897-10-08 1900-01-30 Josef Kirchner Manufacture of electrical resistances.
US1272406A (en) * 1915-10-18 1918-07-16 Nat Carbon Co Inc Void-filled depolarizing mass.
US1293272A (en) * 1915-10-25 1919-02-04 Nat Carbon Co Inc Polymerized manganese-dioxid-depolarizer.
US1296700A (en) * 1917-06-09 1919-03-11 French Battery & Carbon Co Primary battery.
US1637433A (en) * 1925-01-12 1927-08-02 Nat Carbon Co Inc Dry cell
US1724886A (en) * 1925-06-01 1929-08-13 Hartford Empire Co Manufacture of refractory compositions
US2091569A (en) * 1935-09-30 1937-08-31 Norton Co Article of self bonded granular material and method of making the same
US2208185A (en) * 1939-03-28 1940-07-16 Canadian Refractories Ltd Granular magnesia product
US2307301A (en) * 1940-06-18 1943-01-05 Mole Richardson Co Spot lamp

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US642414A (en) * 1897-10-08 1900-01-30 Josef Kirchner Manufacture of electrical resistances.
US1272406A (en) * 1915-10-18 1918-07-16 Nat Carbon Co Inc Void-filled depolarizing mass.
US1293272A (en) * 1915-10-25 1919-02-04 Nat Carbon Co Inc Polymerized manganese-dioxid-depolarizer.
US1296700A (en) * 1917-06-09 1919-03-11 French Battery & Carbon Co Primary battery.
US1637433A (en) * 1925-01-12 1927-08-02 Nat Carbon Co Inc Dry cell
US1724886A (en) * 1925-06-01 1929-08-13 Hartford Empire Co Manufacture of refractory compositions
US2091569A (en) * 1935-09-30 1937-08-31 Norton Co Article of self bonded granular material and method of making the same
US2208185A (en) * 1939-03-28 1940-07-16 Canadian Refractories Ltd Granular magnesia product
US2307301A (en) * 1940-06-18 1943-01-05 Mole Richardson Co Spot lamp

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2739914A (en) * 1954-05-19 1956-03-27 Manganese Chemicals Corp Manganese dioxide depolarizer
FR2356283A1 (en) * 1976-06-23 1978-01-20 Niggl Hans SHIELDING PLATE, FOR ACCUMULATOR

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