WO1997013285A1 - Dry battery having a cathode with additives - Google Patents

Dry battery having a cathode with additives Download PDF

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Publication number
WO1997013285A1
WO1997013285A1 PCT/IT1996/000181 IT9600181W WO9713285A1 WO 1997013285 A1 WO1997013285 A1 WO 1997013285A1 IT 9600181 W IT9600181 W IT 9600181W WO 9713285 A1 WO9713285 A1 WO 9713285A1
Authority
WO
WIPO (PCT)
Prior art keywords
battery according
titanium dioxide
powder
present
cathode
Prior art date
Application number
PCT/IT1996/000181
Other languages
French (fr)
Inventor
Francesco Rizzardi
Original Assignee
Volta Industries S.R.L.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Volta Industries S.R.L. filed Critical Volta Industries S.R.L.
Publication of WO1997013285A1 publication Critical patent/WO1997013285A1/en

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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
    • H01M4/48—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
    • H01M4/62—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
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/04—Cells with aqueous electrolyte

Definitions

  • Dry battery having a cathode with additives
  • the present invention relates to a dry battery of the primary alkaline type. More particularly, the invention relates to a battery including a zinc anode, an anodic gel containing an alkaline compound, and a cathode including a depolarizing mixture based on manganese dioxide and graphite.
  • the object of the present invention is a further increase - by means of particular additives - of the output of the battery, expressed as the duration of discharge before the discharge tension falls below a preset level.
  • the present invention provides for the use as additive of a mica powder whose grains have a surface at least partially coated with titanium dioxide, this powder having a particle size distribution of between 1 and 100 micrometres, preferably between 1 and 15 micrometres.
  • the said powder has a content by weight formed from equal parts of titanium dioxide and mica.
  • Said powder can be present in the depolarizing mixture forming the cathode in a percentage quantity of between 0.1 and 5%, preferably in a percentage quantity of the order of 1%.
  • the titanium dioxide contained in the said powder can be present in any one of its allotropic forms called anatase, rutile and brookite, also in a mixture of these, and is deposited on the mica grains, for example by dispersing the mica in liquid titanium tetrachloride and then transforming, by means of a known thermochemical process, the titanium tetrachloride into titanium oxide of the desired allotropic form.
  • the particular structure of the additive proposed according to the present invention characterized by a high granulometric fineness and, given the particular lamellar configuration of the mica crystals, by a high value of the surface-to-volume ratio of the grains themselves and by surface adhesion of the titanium dioxide particles to the mica particles - provides an increased absorption capacity for liquids and hence electrolyte on the part of the cathodic mass in which the additive is dispersed.
  • the absorption capacity of the electrolyte increases by about 8% when passing from an additive composed solely of titanium dioxide to an additive as described above and composed of mica and titanium dioxide in equal parts.
  • the increased quantity of electrolyte contained in the cathode makes higher discharge outputs possible, both for discharges at high consumption and for other types of use.
  • Figures 1 to 6 show graphs of the discharge of batteries with an additive, respectively, with an additive containing 95% of rutile, the tests for which are marked A in the graphs, and with an additive containing 50% of rutile and 50% of mica mixed with one another in a powder, the tests for which are marked E in the graphs.
  • batteries were prepared comprising: a zinc anode, an anodic gel containing caustic potash, a corrosion inhibitor without added mercury, and a cathode comprising a depolarizing mixture based on manganese dioxide, graphite and the mica powder in which the grains were coated with rutile.
  • a depolarizing mixture said components were intimately mixed with one another beforehand in order to ensure a homogeneous distribution in the mixture.
  • the same constructional criterion was used and the same common components were utilized in order to guarantee the maximum uniformity of the batteries themselves which were produced from a single batch of common materials.
  • the test was carried out with a uniform criterion also with regard to the ageing of the batteries or to the time elapsed from the formation of each battery and the test itself. In all the tests, the concentration of the additive was kept within 1% relative to the manganese dioxide.
  • the values of duration measured show that the batteries of type E (provided with an additive of mica and rutile) give durations which are greater by a value of between 4% and 8% than the durations of the batteries of type A (provided solely with a rutile additive) .

Abstract

The battery is of the primary alkaline type and comprises a zinc anode, an anodic gel and a cathode. The cathode comprises a depolarizing mixture based on manganese dioxide containing a mica powder whose grains have a surface at least partially coated with titanium dioxide.

Description

Dry battery having a cathode with additives
DESCRIPTION
Technical Field
The present invention relates to a dry battery of the primary alkaline type. More particularly, the invention relates to a battery including a zinc anode, an anodic gel containing an alkaline compound, and a cathode including a depolarizing mixture based on manganese dioxide and graphite.
Background Art
The most recent developments regarding the manufacture of primary alkaline manganese batteries involve the use of titanium dioxide in various allotropic forms as an additive in the depolarizing mixture based on manganese dioxide, which represents the cathode of the battery. Such an additive, which enhances the rate of depolarization on the part of the manganese dioxide in the interior of the cathodic mass, principally has the effect of increasing the output of the battery when the latter is subjected to use with high current consumption.
Objects and Summary of the Invention
The object of the present invention is a further increase - by means of particular additives - of the output of the battery, expressed as the duration of discharge before the discharge tension falls below a preset level. In particular, the present invention provides for the use as additive of a mica powder whose grains have a surface at least partially coated with titanium dioxide, this powder having a particle size distribution of between 1 and 100 micrometres, preferably between 1 and 15 micrometres.
In a preferred embodiment, the said powder has a content by weight formed from equal parts of titanium dioxide and mica.
Said powder can be present in the depolarizing mixture forming the cathode in a percentage quantity of between 0.1 and 5%, preferably in a percentage quantity of the order of 1%.
The titanium dioxide contained in the said powder can be present in any one of its allotropic forms called anatase, rutile and brookite, also in a mixture of these, and is deposited on the mica grains, for example by dispersing the mica in liquid titanium tetrachloride and then transforming, by means of a known thermochemical process, the titanium tetrachloride into titanium oxide of the desired allotropic form.
With respect to a cathodic mass provided with an additive of only titanium dioxide, the particular structure of the additive proposed according to the present invention - characterized by a high granulometric fineness and, given the particular lamellar configuration of the mica crystals, by a high value of the surface-to-volume ratio of the grains themselves and by surface adhesion of the titanium dioxide particles to the mica particles - provides an increased absorption capacity for liquids and hence electrolyte on the part of the cathodic mass in which the additive is dispersed. For example, with a quantity of 1% of additive in the depolarizing mixture, the absorption capacity of the electrolyte increases by about 8% when passing from an additive composed solely of titanium dioxide to an additive as described above and composed of mica and titanium dioxide in equal parts. The increased quantity of electrolyte contained in the cathode makes higher discharge outputs possible, both for discharges at high consumption and for other types of use. Brief Description of the Drawings
The invention will be better understood by following the description and the attached drawing which refers to properties useful in the evaluation of the inventive content of the invention. In the drawing: Figures 1 to 6 show graphs of the discharge of batteries with an additive, respectively, with an additive containing 95% of rutile, the tests for which are marked A in the graphs, and with an additive containing 50% of rutile and 50% of mica mixed with one another in a powder, the tests for which are marked E in the graphs.
Detailed Description
For comparison of the effectiveness of the additives, tests were carried out under various discharge conditions, both intermittent and continuous, and with loads of varying magnitude (expressed as the electrical resistance in ohm) .
For the tests, batteries were prepared comprising: a zinc anode, an anodic gel containing caustic potash, a corrosion inhibitor without added mercury, and a cathode comprising a depolarizing mixture based on manganese dioxide, graphite and the mica powder in which the grains were coated with rutile. To obtain the depolarizing mixture, said components were intimately mixed with one another beforehand in order to ensure a homogeneous distribution in the mixture. For all the batteries, the same constructional criterion was used and the same common components were utilized in order to guarantee the maximum uniformity of the batteries themselves which were produced from a single batch of common materials. The test was carried out with a uniform criterion also with regard to the ageing of the batteries or to the time elapsed from the formation of each battery and the test itself. In all the tests, the concentration of the additive was kept within 1% relative to the manganese dioxide.
In Figures 1 to 6, the durations in minutes or in hours of effective discharge are indicated on the abscissae. For each test, the result assumed is the time of actual discharge elapsed until the potential of the battery has fallen to the value E.P. (end point) shown on each figure, in accordance with the standard IEC 86/1. For each type of battery, the right-hand border of the hatched area represents in the figures the average of the values obtained with further successive tests.
In all the tests carried out, the values of duration measured show that the batteries of type E (provided with an additive of mica and rutile) give durations which are greater by a value of between 4% and 8% than the durations of the batteries of type A (provided solely with a rutile additive) .

Claims

1. Dry battery of the primary alkaline type, including: a zinc anode; an anodic gel containing an alkaline compound; and a cathode comprising a depolarizing mixture based on manganese dioxide and graphite, characterized in that said mixture contains a mica powder whose grains are coated at least partially with titanium dioxide.
2. Battery according to Claim 1, characterized in that said powder has a particle size distribution of between 1 and 100 micrometres.
3. Battery according to Claim l or 2 , characterized in that said powder has a particle size distribution of between 1 and 15 micrometres.
4. Battery according to Claims 1 to 3 , characterized in that said powder has a content by weight formed from substantially equal parts of titanium dioxide and mica.
5. Battery according to any of the preceding claims, characterized in that said powder is present in said mixture in a percentage quantity of between 0.1 and 5%.
6. Battery according to Claim 4, characterized in that said percentage quantity is of the order of 1%.
7. Battery according to any of the preceding claims, characterized in that the titanium dioxide is present in the allotropic form called anatase.
8. Battery according to any of Claims l to 5, characterized in that the titanium dioxide is present in the allotropic form called rutile.
9. Battery according to any of Claims 1 to 5, characterized in that the titanium dioxide is present in the allotropic form called brookite.
10. Battery according to any of Claims 1 to 5, characterized in that the titanium dioxide is present as a mixture of said various allotropic forms.
11. Battery according to any of Claims 1 to 10, characterized in that said alkaline compound is caustic potash or magnesium hydroxide or the like.
12. Battery according to any of Claims 1 to 10, characterized in that it includes corrosion inhibitors and/or a mercury amalgam.
PCT/IT1996/000181 1995-10-03 1996-09-30 Dry battery having a cathode with additives WO1997013285A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITFI95A000203 1995-10-03
IT95FI000203A IT1278764B1 (en) 1995-10-03 1995-10-03 DRY STACK WITH ADDITIVED CATHOD

Publications (1)

Publication Number Publication Date
WO1997013285A1 true WO1997013285A1 (en) 1997-04-10

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Country Status (2)

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IT (1) IT1278764B1 (en)
WO (1) WO1997013285A1 (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998015987A1 (en) * 1996-10-10 1998-04-16 Merck Patent Gmbh Modified electrode material and its use
WO1998034289A1 (en) * 1997-01-31 1998-08-06 Merck Patent Gmbh New manganese dioxide electrodes, process for producing the same and their use
US5919588A (en) * 1996-04-20 1999-07-06 Varta Batterie Aktiengesellschaft Cathode additive for alkaline primary cells
US6749964B2 (en) 2000-03-31 2004-06-15 MERCK Patent Gesellschaft mit beschränkter Haftung Active positive-electrode material in electrochemical cells, and process for the production of these materials
ES2209656A1 (en) * 2002-12-13 2004-06-16 Celaya Emparanza Y Galdos, S.A. (Cegasa) Electrochemical Element or Cell and Cathode thereof
US6756115B2 (en) 2000-11-30 2004-06-29 Em Industries, Inc. 3D structural siliceous color pigments
EP2420514A1 (en) 2006-08-03 2012-02-22 MedImmune Limited Targeted binding agents directed to PDGFR-alpha and uses thereof
US20140370376A1 (en) * 2012-12-20 2014-12-18 Panasonic Corporation Alkaline battery

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59194355A (en) * 1983-03-30 1984-11-05 Toshiba Battery Co Ltd Manufacture of manganese dry battery
US5300371A (en) * 1990-03-23 1994-04-05 Battery Technologies Inc. Manganese dioxide positive electrode for rechargeable cells, and cells containing the same
US5342712A (en) * 1993-05-17 1994-08-30 Duracell Inc. Additives for primary electrochemical cells having manganese dioxide cathodes

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59194355A (en) * 1983-03-30 1984-11-05 Toshiba Battery Co Ltd Manufacture of manganese dry battery
US5300371A (en) * 1990-03-23 1994-04-05 Battery Technologies Inc. Manganese dioxide positive electrode for rechargeable cells, and cells containing the same
US5342712A (en) * 1993-05-17 1994-08-30 Duracell Inc. Additives for primary electrochemical cells having manganese dioxide cathodes

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 009, no. 053 (E - 301) 7 March 1985 (1985-03-07) *

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5919588A (en) * 1996-04-20 1999-07-06 Varta Batterie Aktiengesellschaft Cathode additive for alkaline primary cells
US6348259B1 (en) 1996-10-10 2002-02-19 Merck Patent Gesellschaft Mit Modified electrode material and its use
WO1998015987A1 (en) * 1996-10-10 1998-04-16 Merck Patent Gmbh Modified electrode material and its use
WO1998034289A1 (en) * 1997-01-31 1998-08-06 Merck Patent Gmbh New manganese dioxide electrodes, process for producing the same and their use
US6337160B1 (en) 1997-01-31 2002-01-08 Merck Patent Gesellschaft Mit Beschrankter Manganese dioxide electrodes, process for producing the same and their use
US6749964B2 (en) 2000-03-31 2004-06-15 MERCK Patent Gesellschaft mit beschränkter Haftung Active positive-electrode material in electrochemical cells, and process for the production of these materials
US6756115B2 (en) 2000-11-30 2004-06-29 Em Industries, Inc. 3D structural siliceous color pigments
ES2209656A1 (en) * 2002-12-13 2004-06-16 Celaya Emparanza Y Galdos, S.A. (Cegasa) Electrochemical Element or Cell and Cathode thereof
EP2420514A1 (en) 2006-08-03 2012-02-22 MedImmune Limited Targeted binding agents directed to PDGFR-alpha and uses thereof
EP2420513A1 (en) 2006-08-03 2012-02-22 MedImmune Limited Targeted binding agents directed to PDGFR-alpha and uses thereof
US20140370376A1 (en) * 2012-12-20 2014-12-18 Panasonic Corporation Alkaline battery
EP2768048A4 (en) * 2012-12-20 2016-04-27 Panasonic Ip Man Co Ltd Alkaline cell
US9337485B2 (en) * 2012-12-20 2016-05-10 Panasonic Intellectual Property Management Co., Ltd. Alkaline battery

Also Published As

Publication number Publication date
IT1278764B1 (en) 1997-11-27
ITFI950203A1 (en) 1997-04-03
ITFI950203A0 (en) 1995-10-03

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