CN100472861C - Manganese dry cell - Google Patents

Manganese dry cell Download PDF

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Publication number
CN100472861C
CN100472861C CNB2005800126988A CN200580012698A CN100472861C CN 100472861 C CN100472861 C CN 100472861C CN B2005800126988 A CNB2005800126988 A CN B2005800126988A CN 200580012698 A CN200580012698 A CN 200580012698A CN 100472861 C CN100472861 C CN 100472861C
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paste
bismuth
dry cell
layer
manganese dry
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CN1947295A (en
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坂元光洋
石田努
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Panasonic Holdings Corp
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Matsushita Electric Industrial Co Ltd
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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
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/04—Cells with aqueous electrolyte
    • H01M6/06—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid
    • H01M6/08—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid with cup-shaped electrodes
    • 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
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
    • H01M6/168—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by additives
    • 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
    • H01M6/22—Immobilising of electrolyte
    • 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

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Primary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Prevention Of Electric Corrosion (AREA)

Abstract

Disclosed is a manganese dry cell having excellent discharge characteristics and storage characteristics wherein corrosion resistance of the anode can is maintained for a long time from the beginning. In such a manganese dry cell, the electrolyte solution in the paste layer contains not less than 10 weight% of ammonium chloride and the paste layer contains bismuth in an amount equivalent to 0.0005-0.5 weight% of the electrolyte solution contained in the paste layer.

Description

Manganese dry cell
Technical field
The present invention relates to a kind of no mercury manganese dry cell, particularly relate to a kind of aspect discharge performance and storge quality improved paste formula manganese dry cell.
Background technology
Traditionally, in sticking with paste the formula manganese dry cell, in sticking with paste layer, add the mercury compound mercury chloride for example that content is 0.01-0.1wt% in order to suppress self discharge.By adding the corrosion that such mercury compound can prevent the zinc tube, because the surface of zinc is by amalgamation and remain under the high hydrogen overvoltage state.
Yet,, need eliminate the use of mercury in the paste formula manganese dry cell along with increase day by day to global problem of environmental pollution understanding.Do not use mercury and improve the method for negative pole zinc tube corrosion resistance as a kind of, proposed in sticking with paste layer, to add inidum chloride (for example, with reference to the open No.H06-163019 of Japanese unexamined patent publication No.).
By this method, in order to improve the corrosion resistance of negative pole tube, the negative pole tube uses the kirsite that contains 0.4wt% lead usually.At this, if consider environmental factor content plumbous in the negative pole tube is dropped to less than 0.4wt%, must add inidum chloride in a large number so to keep the corrosion resistance of negative pole tube.The result is that the surface coverage of negative pole tube has the indium coating, internal resistance increase, discharge performance decline.In addition, because the increase of the amount of the inidum chloride that uses causes cost to increase.
Summary of the invention
Problem to be solved by this invention
Consider the problems referred to above relevant with prior art, the object of the present invention is to provide a kind of manganese dry cell with excellent discharge performance and good storge quality, this manganese dry cell need not to use mercury or plumbous and the corrosion resistance of negative pole tube can be kept the time period longer than its starting stage.
The method of dealing with problems
Manganese dry cell according to the present invention comprises: the cathode mix that comprises manganese dioxide; The negative pole tube that comprises zinc; The paste layer that comprises starch, water-soluble pastes and electrolyte, this paste layer is used for separating described cathode mix and described negative pole tube, wherein the described electrolyte of sticking with paste in the layer comprises the ammonium chloride that its content is not less than 10wt%, and stick with paste layer and comprise bismuth, the content of this bismuth equals to stick with paste the 0.0005-0.5wt% of electrolyte contained in the layer.
The bismuth that preferably contains is the form of bismuth compound.
Preferred bismuth compound is to be selected from least a in bismuth chloride and the bismuth oxide.
The preferred layer of sticking with paste also comprises inidum chloride, and the content of the indium that it contains equals to stick with paste the 0.001-0.5wt% of contained electrolyte in the layer.
Preferably, the negative pole tube is by zinc or do not comprise plumbous kirsite and make.
The invention effect
According to the present invention, a kind of manganese dry cell with excellent discharge performance and good storge quality is provided, this manganese dry cell need not to use mercury or plumbous and the corrosion resistance of negative pole tube can be kept the time period longer than its starting stage.
Description of drawings
Fig. 1 is the front elevation according to the part cross section of the manganese dry cell of the embodiment of the invention.
Embodiment
The invention is characterized in, provide the paste layer that is used as being used to separating negative pole and anodal dividing plate to contain bismuth in the manganese dry cell.Stick with paste layer and comprise starch, water-soluble pastes and electrolyte.Electrolyte is the aqueous solution of zinc chloride and ammonium chloride.Bismuth adds to the form of bismuth compound to be stuck with paste in the layer.For example, the water-soluble pastes of use is made by the polyethylene glycols alkyl phenol.
Consider the ammonium ion reaction in bismuth compound and the electrolyte, and the form with the ammonium salt of bismuth exists in sticking with paste layer.Along with bismuth metal and metallic zinc are carried out ion-exchange reactions at zinc surface, ammonium salt deposits rapidly, thereby the hydrogen overvoltage of zinc surface rises.Like this, the same effect that has the corrosion of prevention zinc negative pole tube and suppress self discharge of bismuth compound with mercury.
The electrolyte of sticking with paste in the layer comprises the ammonium chloride that content is not less than 10wt%; Stick with paste layer and comprise the bismuth that content equals to stick with paste the 0.0005-0.5wt% of contained electrolyte in the layer.In this case, can obtain good discharge performance; Especially, even, therefore improved storge quality owing to after having stored the long time section, still keep good discharge performance.
If the content of bismuth surpasses 0.5wt%, internal resistance increase and discharge performance descend.On the other hand, if the content of bismuth, just can not obtain effect of sufficient less than 0.0005wt% to stop the corrosion of negative pole tube.
Preferably, bismuth compound is select from the group who is made of bismuth chloride and bismuth oxide at least a.BiCl 3Can be used as an example of bismuth chloride.Bi 2O 3Can be used as an example of bismuth oxide.
In addition, if the concentration of ammonium chloride is less than 10wt% in the electrolyte, because bismuth is difficult to be dissolved in the electrolyte, the amount that therefore is deposited on the bismuth on the negative pole tube just descends, and adds the effect of bismuth with the corrosion resistance of improving the negative pole tube thereby reduced.
Preferably, stick with paste layer and also comprise inidum chloride, the amount of its contained indium equals to stick with paste the 0.001-0.5wt% of contained electrolyte in the layer.
When in sticking with paste layer, only adding bismuth compound, compare with the situation of adding mercury, the variation of voltage is tended to raise more or less in the product, but when except adding bismuth compound, also adding inidum chloride, because the surface of negative pole tube evenly is coated with the layer that contains indium and bismuth, so the variation of voltage will be reduced to and roughly the same level when adding mercury.
Infer and add the variation that indium can suppress voltage and be following mechanism.
When the ammonium salt of bismuth was present in the electrolyte, bismuth metal preferably was deposited on the surface of zinc negative pole tube.Bismuth metal has poor ductility and low electronic conductivity.Yet, believe that the indium metal with high ductibility and high electronic conductivity deposits with bismuth, and the surface of zinc negative pole tube evenly is coated with these two kinds of metals to obtain stable corrosion resistance when bismuth and indium all exist.
The example of inidum chloride comprises InCI, InCl 3, In 2Cl 3, In 4Cl 7And In 5Cl 9Halide for other also has identical effect, and this halid example comprises InBr 3, InF 3And InI 3
Traditionally, use the kirsite that contains 0.4wt% lead, to improve the corrosion resistance of negative pole tube as the negative pole tube.Yet; consider environmental protection; when lead content descends or adds when plumbous, therefore the also negative pole tube that can have good corrosion resistance by using above-mentioned paste layer to obtain just can obtain to have the paste formula manganese dry cell of excellent discharge performance and good storge quality.That is to say,, thereby can provide a kind of mercury or plumbous environment amenable paste formula manganese dry cell of not using according to the present invention.
Embodiment
The detailed hereafter embodiments of the invention.
" embodiment 1 to 4 and comparative example 1 to 3 "
Whether the method validation bismuth below adopting is dissolved in the electrolyte solution.
By preparing electrolyte with mixed zinc chloride, ammonium chloride and the water shown in the table 1.In electrolyte, add BiCl with respect to the 0.1wt% of zine plate weight with content 3Or Bi 2O 3The bismuth of form then stirs.Then, zine plate is dipped in the electrolyte solution.In electrolyte, place after 1 hour, calculate the amount of the bismuth that deposits to the zine plate surface.The result is as shown in table 1.
Table 1
Figure C200580012698D00061
Can find, be not less than under the situation of 10wt% at the content of the ammonium chloride that electrolyte contains, when bismuth is BiCl 3The time, the deposition of bismuth is not less than 0.06wt%, when bismuth is Bi 2O 3The time, the deposition of bismuth is not less than 0.04wt%.On the other hand, when the concentration of ammonium chloride during less than 10wt%, the deposition of bismuth is not more than 0.01wt%.Expression: when the concentration of ammonium chloride during less than 10wt%, bismuth is difficult to be dissolved in the electrolyte solution, therefore, is difficult to be deposited on the zine plate.
After 24 hours and among the embodiment 4 after 96 hours, bismuth almost completely is deposited on the zine plate in embodiment 1 to 3.This causes finding the following fact, and when using that wherein the concentration of ammonium chloride is not less than the electrolyte of 10wt%, bismuth is dissolved in the electrolyte fully, the result, and bismuth can almost completely be deposited on the zine plate, therefore can effectively utilize.
" embodiment 5 to 23 and comparative example 4 to 7 "
(1) is used to form the preparation of the paste of sticking with paste layer
Prepare electrolyte according to the mixed zinc chloride of the ratio of weight ratio 10:20:70, ammonium chloride and water.Then, according to mixed electrolyte, starch powder and the water-soluble pastes of weight ratio 75:24:1, prepare and be used to form the paste of sticking with paste layer by in the gained mixture, adding compound with the amount of the amount of the relative electrolyte shown in the table 2.In the table 2, the InCl of interpolation is shown by the amount that its amount is changed into indium or bismuth respectively 3, BiCl 3And Bi 2O 3Amount.
Table 2
Figure C200580012698D00081
(2) preparation of paste formula manganese dry cell
Prepare paste formula manganese dry cell according to following processes.The front elevation of paste formula manganese dry cell of the present invention partly is shown in the cross-sectional view of Fig. 1.
Contain kirsite cast molding in having the cylinder of closed bottom end of 0.4wt% lead, to form negative pole tube 3.After on the bottom of the inner surface that base stock 5 is placed on negative pole tube 3, be filled in the negative pole tube 3 being used to form the paste of sticking with paste layer.Then, the carbon-point 1 that forms by the sintering carbon dust inserts in the cathode mix 2, and this cathode mix 2 is placed on the inside of negative pole tube 3, therefore forms to stick with paste layer 4 and be clipped in such structure between cathode mix 2 and the negative pole tube 3.Mix manganese dioxide, prepare cathode mix 2 according to the weight ratio of 50:10:40 as the acetylene black of electric conducting material with as the aqueous solution that contains the 30wt% zinc chloride of electrolyte as active material.
The hole that is used to insert carbon-point 1 is formed on the center of the seal 9 that is formed by polyolefin resin.Under pressure, carbon-point 1 is inserted the hole of passing seal 9, thereby the outer rim of seal 9 is fixed in the edge of openend of negative pole tube 3.Then, positive terminal 6 is fixed to the top of carbon-point 1, i.e. positive electrode collector.
The periphery that provides the pitch tube 11 of insulation to be placed on negative pole tube 3 by the collapsible resin film of heat being used to of forming, the upper part of this film end portion that covers the upper surface of outer peripheral portion of seal 9 and this film covers the lower surface of sealing ring 13 simultaneously.Place sealing plate 7 to cover seal 9.
The positive terminal of being made by sheet tin 6 forms the shape with hat core and tabular marginal portion, and this hat core covers the upper part of carbon-point 1.Provide the dead ring 8 that is formed from a resin so that positive terminal 6 and sealing plate 7 are separated in the marginal portion of positive terminal 6.Provide also base plate 10 in the bottom surface of negative pole tube 3, and sealing ring 13 is installed around the outer surface of the tabular periphery of base plate 10 as negative terminal.
The outside envelope 12 that the column type sheet tin forms is placed on the periphery of pitch tube 11.The end portion of outside envelope 12 curves inwardly, and inwardly curls in its upper part.In addition, the top ca(u)lk of upper part to the peripheral edge of sealing plate 7 to obtain manganese dry cell.
Evaluation and test
(1) evaluation and test of initial performance
After battery was made, each battery discharged under the load of 2.2 Ω immediately, measured discharge time.End voltage is set to 0.8V.Tested five samples, with its mean value as battery discharge time.If be 125 minutes or longer discharge time, judge that so battery has good discharge performance.
(2) evaluation and test of storge quality
Measure the voltage of battery after battery is made immediately, storage batteries is 12 months under the room temperature.Store after 12 months, remeasure the voltage of battery, to check how many cell voltages descended from initial voltage between the storage life.Tested 100 samples, with its mean value as battery voltage drop.If the amount of battery voltage drop is 45mV or still less, judge that so battery has good storge quality.
In addition, obtain the deviation of cell voltage in the different samples for the battery after storing.Tested 100 samples, the difference between the highest cell voltage of acquisition and the minimum cell voltage is as deviation.
The results are shown in the table 3.
Table 3
Initial discharge performance (min) Store back battery voltage drop (mV) Store the deviation (mV) of back cell voltage
Comparative example 4 119 60 1.8
Comparative example 5 129 45 1.2
Comparative example 6 136 56 2.2
Embodiment 5 142 36 2.3
Embodiment 6 140 36 2.4
Embodiment 7 141 35 2.4
Embodiment 8 140 34 2.5
Embodiment 9 140 34 2.5
Embodiment 10 141 33 2.5
Embodiment 11 140 33 2.6
Comparative example 7 121 33 2.6
Embodiment 12 139 36 2.3
Embodiment 13 138 34 2.5
Embodiment 14 140 35 2.3
Embodiment 15 139 38 1.2
Embodiment 16 139 37 1.1
Embodiment 17 138 37 1.1
Embodiment 18 138 37 1.0
Embodiment 19 137 36 1.0
Embodiment 20 137 36 1.1
Embodiment 21 114 36 1.1
Embodiment 22 137 39 1.1
Embodiment 23 135 37 1.0
Performance when (A) adding bismuth compound in the paste layer
In the comparative example 5, the raising of negative pole tube corrosion resistance has surpassed comparative example 4, and the amount of battery voltage drop reduces between the storage life, and the deviation that stores the back cell voltage also descends.
In embodiment 5 to 13, to stick with paste in the layer and added bismuth compound, the raising of negative pole tube corrosion resistance has surpassed comparative example 5, and the amount of battery voltage drop further reduces between the storage life.In addition, compare, in embodiment 5 to 13, obtain good initial performance with comparative example 5.In comparative example 7, because the bi content height, so internal resistance increase and discharge performance decay.In comparative example 6, because bi content is low, thus the corrosion resistance deficiency of negative pole tube, so the amount of battery voltage drop increases between the storage life.
Performance when (B) in containing the paste layer of bismuth compound, adding inidum chloride
In embodiment 14 to 23, in containing the paste layer of bismuth compound, add inidum chloride, the corrosion resistance of negative pole tube improves, and the amount of battery voltage drop reduces between the storage life.In embodiment 14, because the amount of the inidum chloride that adds is few, so also little to the inhibitory action that stores back cell voltage deviation.In embodiment 21, suppressed to store the deviation of back cell voltage, still, because the amount of the inidum chloride that adds is big, so internal resistance increases the guiding discharge performance degradation.In embodiment 15 to 20,22 and 23, the storge quality that the initial discharge performance that obtains is become reconciled, the deviation of cell voltage after having suppressed simultaneously to store.
" embodiment 24 to 39 and comparative example 8 to 9 "
Use with embodiment 5 in identical method prepare paste formula manganese dry cell, except content plumbous in the negative pole tube and stick with paste the bismuth chloride of interpolation in the layer and the amount of inidum chloride such as table 4 shown in change, and evaluated and tested their initial performance and storge quality.In the table 4, the InCl of interpolation is shown respectively by the amount that converts indium or bismuth to 3And BiCl 3Amount.The results are shown in the table 5.
Table 4
Figure C200580012698D00131
Table 5
Initial discharge performance (min) Store back battery voltage drop (mV) Store the deviation (mV) of back cell voltage
Embodiment 24 141 38 2.3
Embodiment 25 142 40 2.2
Embodiment 26 142 41 2.3
Comparative example 8 144 63 2.0
Embodiment 27 143 43 2.5
Embodiment 28 143 42 2.4
Embodiment 29 143 42 2.4
Embodiment 30 143 41 2.5
Embodiment 31 142 40 2.5
Embodiment 32 142 39 2.6
Comparative example 9 123 38 2.7
Embodiment 33 142 42 2.2
Embodiment 34 141 45 1.0
Embodiment 35 141 45 1.2
Embodiment 36 140 44 1.0
Embodiment 37 140 44 0.9
Embodiment 38 139 43 1.2
Embodiment 39 116 43 1.1
(C) plumbous content and the performance when in sticking with paste layer, adding bismuth compound in reducing the negative pole tube
In comparative example 8, because bi content is low, stop the effect of negative pole tube corrosion insufficient, therefore, battery voltage drop is very big between the storage life.In comparative example 9, because the bi content height, so thereby internal resistance increases and the initial discharge performance degradation.
On the other hand, among the embodiment 22 to 24 that lead content reduces in the negative pole tube, in not comprising plumbous embodiment 27 to 32, by adding the storge quality that initial discharge performance that a spot of bismuth obtains is become reconciled.
(D) lead content reduces and contains performance when having added inidum chloride in the paste layer of bismuth compound in the negative pole tube
In not comprising plumbous embodiment 34 to 38, obtained the storge quality that good initial discharge performance is become reconciled by adding a spot of bismuth, meanwhile,, suppressed to store the deviation of back cell voltage owing to added inidum chloride.
In embodiment 33, because the amount of the inidum chloride that adds is few, so also little to the inhibitory action that stores back cell voltage deviation.In embodiment 39, suppressed to store the deviation of back cell voltage, still, and because the amount of the inidum chloride that adds is many, thus the internal resistance increase, thus the guiding discharge performance degradation.
Commercial Application
According to top description, paste-type manganese dry cell of the present invention has good discharge performance and good storge quality, therefore can be used as the power supply of the equipment such as high performance mini electronic equipment, portable set.

Claims (6)

1, a kind of paste formula manganese dry cell comprises: the cathode mix that comprises manganese dioxide; The negative pole tube that comprises zinc; And the paste layer that comprises starch, water-soluble pastes and electrolyte, this paste layer is used for separating described cathode mix and described negative pole tube, wherein
The described described electrolyte of sticking with paste in the layer comprises the ammonium chloride that its content is not less than 10wt%, and described paste layer comprises content and equals the described bismuth of sticking with paste the 0.0005-0.05wt% of the described electrolyte that contains in the layer,
Described paste layer comprises that also the inidum chloride that contains indium, the content of described indium equal the described 0.001-0.5wt% that sticks with paste the described electrolyte that contains in the layer, and
Described negative pole tube is made by lead-free zinc or kirsite.
2, paste formula manganese dry cell according to claim 1, wherein the form with bismuth compound contains described bismuth.
3, paste formula manganese dry cell according to claim 2, wherein said bismuth compound are at least a for what select from the group who is made of bismuth chloride and bismuth oxide.
4, paste formula manganese dry cell according to claim 1, wherein said paste layer comprise content and equal the described bismuth of sticking with paste the 0.005-0.05wt% of the described electrolyte that contains in the layer.
5, paste formula manganese dry cell according to claim 1 comprises the ammonium chloride that its content is 10-25wt% in the described electrolyte in the wherein said paste layer.
6, paste formula manganese dry cell according to claim 1, wherein said water-soluble pastes is the polyethylene glycols alkyl phenol.
CNB2005800126988A 2004-06-28 2005-06-21 Manganese dry cell Expired - Fee Related CN100472861C (en)

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EP1892778A4 (en) * 2005-08-09 2009-02-04 Panasonic Corp Manganese dry cell
US8974973B2 (en) * 2010-05-27 2015-03-10 Wing Fai Leung Starch-based battery system

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JP3651852B2 (en) * 1992-07-01 2005-05-25 東芝電池株式会社 Manganese battery
JP2964802B2 (en) * 1992-11-19 1999-10-18 松下電器産業株式会社 Glue-type manganese dry battery
JPH06325771A (en) * 1993-05-14 1994-11-25 Toshiba Battery Co Ltd Manganese dry cell

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