Chemistry: electrical current producing apparatus – product – and – Current producing cell – elements – subcombinations and... – Electrode
Reexamination Certificate
1999-06-14
2001-06-26
Langel, Wayne (Department: 1754)
Chemistry: electrical current producing apparatus, product, and
Current producing cell, elements, subcombinations and...
Electrode
C429S206000, C429S224000, C429S226000, C429S232000
Reexamination Certificate
active
06251539
ABSTRACT:
FIELD OF THE INVENTION
The invention relates to alkaline cells having a cathode comprising manganese dioxide. The invention relates particularly to an alkaline cell having an anode comprising zinc, a cathode comprising manganese dioxide, and an electrolyte comprising potassium hydroxide wherein the anode includes electrically conductive additives such as metallic powders, particularly tin powder.
BACKGROUND
The cell contents of a primary alkaline cell typically contain an anode comprising zinc anode active material, alkaline electrolyte, a cathode comprising manganese dioxide cathode active material, and an electrolyte ion permeable separator, typically comprising a nonwoven material containing cellulosic fibers and polyvinylalcohol fibers. The anode active material comprises zinc particles admixed with zinc oxide and conventional gelling agents, such as carboxymethylcellulose or acrylic acid copolymers, and electrolyte. The gelling agent holds the zinc particles in place and in contact with each other. A conductive metal nail, known as the anode current collector, is typically inserted into the anode material in contact with the end cap which forms the cell's negative terminal. The alkaline electrolyte is typically an aqueous solution of potassium hydroxide, but other alkali solutions of sodium or lithium hydroxide may also be employed. The cathode material is typically of manganese dioxide and may include small amounts of carbon or graphite to increase conductivity. Conventional alkaline cells have solid cathodes comprising battery grade particulate manganese dioxide. Battery grade manganese dioxide as used herein refers to manganese dioxide generally having a purity of at least about 91 percent by weight. Electrolytic MnO
2
(EMD) is the preferred form of manganese dioxide for alkaline cells because of its high density and since it is conveniently obtained at high purity by electrolytic methods. EMD is typically manufactured from direct electrolysis of a bath of manganese sulfate and sulfuric acid.
In the cathodes of conventional Zn/MnO
2
alkaline cells the manganese dioxide composition is typically between about 70 and 87 percent by weight. Particulate graphite and aqueous KOH solution (7-11 Normal) can be added to the manganese dioxide to form a cathode mixture. Such mixtures form a moist solid mix which can be fully compacted into the cell casing using plungers or other such compacting devices forming a compacted solid cathode mass in contact with the cell casing. The cathode material can be preformed into the shape of disks forming annular rings inserted into the cell in stacked arrangement, for example, as shown in U.S. Pat. No. 5,283,139, and then recompacted.
Since commercial cell sizes are fixed, it has been desirable to attempt to increase the capacity, i.e., the useful service life of the cell, by increasing the surface area of the electrode active material and by packing greater amounts of the active material into the cell. This approach has practical limitations. If the active material is packed too densely into the cell, this can reduce the rate of electrochemical reaction during discharge, in turn reducing service life. Other deleterious effects such as polarization can occur, particularly at high current drain (high power applications). Polarization limits the mobility of ions within the electrode active material and within the electrolyte, which in turn reduces service life. The contact resistance between the MnO
2
cathode active material and the cell casing of an alkaline cell also reduces service life. Such contact resistance losses typically increases, particularly as the cell is discharged during high power applications (between about 0.5 and 1 watt).
There are increasing commercial demands to make primary alkaline cells better suitable for high power application. Modern electronic devices such as cellular phones, digital cameras and toys, flash units, remote control toys, camcorders and high intensity lamps are examples of such high power applications. Such devices require high current drain rates, typically pulsed drain, of between about 0.5 and 2 Amp, more usually between about 0.5 and 1.5 Amp. Correspondingly, they require operation at power demands between about 0.5 and 2 Watt. Modern electronic devices such as cellular phones, digital cameras and toys, flash units, remote control toys, camcorders and high intensity lamps are examples of such high power applications. Thus, it is desirable to provide a way of reliably increasing the useful service life of conventional primary alkaline cells particularly for cells to be used in high power applications, without significantly increasing polarization effects or otherwise adversely affecting cell performance.
U.S. Pat. No. 5,240,793 discloses an alkaline cell wherein the zinc in the anode is alloyed with indium and bismuth. The zinc may also be alloyed with indium, bismuth and barium. The cell is substantially free of mercury and has a lead content of less than 30 ppm.
Japanese patent publication Hei 61-2270 discloses the addition of metal powders to the anode of alkaline cells having an anode comprising zinc and a cathode comprising silver oxide (Zn/Ag
2
O cell) . The metal powders have an average particle size between about 0.01 and 5 micron. The types of metal powders disclosed are copper, silver, gold, tin and lead. The zinc is amalgamated with mercury. The metal powders are amalgamated with mercury and can also be treated with anticorrosive agents before being added to the anode. The Zn/Ag
2
O cell is chemically very different from the Zn/MnO
2
cell and has different discharge characteristices. For example, the Zn/Ag
2
O cell does not consume water during discharge, has a flat voltage discharge profile and characteristically higher bulk density of zinc (lower electrolyte loading) in the anode than the Zn/MnO
2
cell.
REFERENCES:
patent: 4968569 (1990-11-01), Chiba et al.
patent: 5240793 (1993-08-01), Glaeser
patent: 5464709 (1995-11-01), Getz et al.
patent: 5607796 (1997-03-01), Jacus et al.
patent: 5639578 (1997-06-01), Urry
patent: 5800939 (1998-09-01), Mishina et al.
patent: 61-2270 (1986-01-01), None
Brys Barbara
Harris Peter B.
Douglas Paul I.
Josephs Barry D.
Krivulka Thomas G.
Langel Wayne
Strickland Jonas N.
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