CN102163700B - Electrochemical device - Google Patents
Electrochemical device Download PDFInfo
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- CN102163700B CN102163700B CN2011100569324A CN201110056932A CN102163700B CN 102163700 B CN102163700 B CN 102163700B CN 2011100569324 A CN2011100569324 A CN 2011100569324A CN 201110056932 A CN201110056932 A CN 201110056932A CN 102163700 B CN102163700 B CN 102163700B
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- 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
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- Y02E60/10—Energy storage using batteries
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Abstract
An electrochemical device, such as an alkaline battery, that is excellent in leakage-resistance and storage characteristics is provided by controlling at least one of the following two conditions with respect to at least the inner side surface of a battery case comprising a nickel plated steel plate. The two conditions are: (1) the intensity ratio of Fe to Ni (IFe/Ni) as determined by electron probe microanalysis; and (2) the ratio of the area with an intensity ratio of Fe to Ni (IFe/Ni) of greater than 1.0 as determined by electron probe microanalysis to the whole area.
Description
The application is to be on July 26th, 2007 applying date, and denomination of invention is " electrochemical appliance ", and application number is dividing an application of 200710136982.7 Chinese invention patent application.
Technical field
The present invention relates to electrochemical appliance, for example comprise the mixture of hydroxy nickel oxide, manganese dioxide or hydroxy nickel oxide and manganese dioxide as the alkaline battery of positive electrode active materials.
Background technology
Alkaline battery is a class electrochemical appliance, and it comprises battery case, cathode mix (positive pole), comprises the gelling negative pole of zinc or kirsite, separates barrier film and alkaline electrolyte anodal and the gelling negative pole.
Recently, the load by the battery-powered device of alkaline electro is increasing always.The alkaline battery that therefore, need to have the flash-over characteristic excellence.A kind of method that has been used for improving the battery discharge characteristic is to mix hydroxy nickel oxide to improve positive electrode potential in cathode mix.
The battery case of this alkaline battery is made by the steel plate with nickel coating usually.The inner surface of battery case inevitably has the zone that slightly exposes Fe.It is difficult particularly suppressing to form this Fe exposed region when the thickness that reduces nickel coating comes cutting down cost.
By positive pole, barrier film, negative pole and alkaline electrolyte etc. being put into battery case and the sealed cell shell opener is made alkaline battery.If the battery case inner surface has the Fe exposed region, Fe therefrom dissolving gradually after battery manufacture, thereby the oxide coating of formation possibility partial coverage battery case inner surface.As a result, the conductivity of inside battery reduces and internal resistance increases, thereby flash-over characteristic reduces when long term storage after battery manufacture (storage characteristics, particularly high-multiplying-power discharge performance reduce).
In addition, the Fe ion that dissolves from the Fe exposed region may move battery and may deposit on the zinc surface of negative pole, forms local cell.Result, produce hydrogen on zinc surface, and the hydrogen reducing manganese dioxide that produces and hydroxy nickel oxide (positive electrode active materials), thereby reduced battery capacity and caused that when long term storage after battery manufacture flash-over characteristic reduces (storage characteristics, particularly high magnification and low range flash-over characteristic reduce).In addition, if the gas build that produces, cell internal pressure (interior pressure) rises, and discharges gas thereby open explosion-proof valve, with break (anti-leakage characteristic reduces) that prevents from causing leaking.
Summary of the invention
But, use traditional nickel-clad steel plate can not suppress fully forming of the oxide coating that caused by the Fe exposed region and local cell, can not improve anti-leakage and storage characteristics.Therefore, one aspect of the present invention is the electrochemical appliance of a kind of anti-leakage and storage characteristics excellence, for example alkaline battery.
The inventor conducts in-depth research the nickel steel plate that is used for forming battery case.As a result, they find to become by control the nickel coating of nickel-clad steel plate on the surface of battery case inner surface, can realize a kind of electrochemical appliance of unconsummated anti-leakage and storage characteristics excellence also so far.
More particularly, the inventor has been found that the inner surface for the battery case that is formed by nickel-clad steel plate, and at least one can obtain the electrochemical appliance of anti-leakage and storage characteristics excellence by controlling following two conditions.Two conditions are: the strength ratio of (1) Fe and Ni; And (2) Fe and Ni strength ratio are greater than 1.0 area and the ratio of whole area.Can determine strength ratio by electron probe microanalysis (EPMA).
" electron probe microanalysis (EPMA) " used herein refers to accelerated electron beam irradiation (namely by electron-beam excitation) material sample, based on the characteristic X-ray spectrum from its emission, detect and identify the element of the microcell that consists of electron beam irradiation and determine the analytical method of the ratio (concentration) of various Constitution Elements.In one aspect of the invention, the inner surface that has at least the battery case of nickel coating with the accelerated electron beam irradiation.Be called EPMA below electron probe microanalysis (EPMA).
" Fe that is determined by electron probe microanalysis (EPMA) and the strength ratio of Ni " used herein refers to belong to according to EPMA the intensity (I of Fe
Fe) with belong to the intensity (I of Ni
Ni) ratio.This is called " strength ratio I below ratio
Fe/Ni".
In addition, be called " having rate " or " strength ratio I below " Fe that is determined by electron probe microanalysis (EPMA) and the strength ratio of Ni greater than 1.0 zone and the ratio in whole zone "
Fe/NiZone greater than 1.0 have a rate ".
Especially, in one aspect of the invention, the following EPMA that carries out for example.At first, cut out approximately the sample of 1cm of 1cm * approximately from the nickel-clad steel plate that consists of battery case.Then, arrange in electron probe microanalyzer under sample and condition below and measure.
Accelerating voltage: 15kV
The amount of electron beam (line): 0.05 μ A
Every point measurement time: 30ms
Every point measurement scope (1 pixel): 2 μ m
Every some range of exposures (probe diameter): 1 μ m or less
In order to detect ferro element, the L alpha ray (wavelength of one of counting ferro element characteristic X-ray
), and use this counting as the intensity I of iron
FeIn addition, in order to detect nickel element, the K alpha ray of counting nickel
And use this counting as the intensity I of nickel
Ni
In order to obtain strength ratio I
Fe/Ni(condition (1)) and have rate (condition (2)), for example, the data that following processing obtains from above-mentioned measuring condition.Specifically, at the lower characteristic X-ray of Fe and the characteristic X-ray of Ni measured of set point (zones of 2 μ m * 2 μ m), and based on the count value of characteristic X-ray, calculate the strength ratio I at this some place
Fe/NiIn measuring a sample, for example locate to carry out this measurement at 86700 points (255 point=86700, point * 340 point) in the area of 510 μ m * 680 μ m.Calculate all points strength ratio I
Fe/NiMean value, and use this mean value as the strength ratio I of one aspect of the invention
Fe/Ni
In addition, the statistical analysis strength ratio I that obtains like this
Fe/NiObtain frequency distribution, and obtain strength ratio I
Fe/NiGreater than 1.0 count and all ratios of counting.Should be understood that the battery-shell surface of being made by iron plate has the crack of tens microns (μ m).Therefore, the measuring range of wishing at every is 5 μ m or less, and total measurement area is 500 μ m * 500 μ m or larger.
One aspect of the present invention provides a kind of electrochemical appliance, and it comprises: the positive pole that comprises the positive electrode active materials in the mixture that is selected from hydroxy nickel oxide, manganese dioxide and hydroxy nickel oxide and manganese dioxide; Comprise the zinc component as the negative pole of negative active core-shell material; Be inserted in the barrier film between positive pole and negative pole; Alkaline electrolyte; And the battery case that holds positive pole, negative pole, barrier film and alkaline electrolyte.Battery case is comprised of the nickel-clad steel plate that has nickel coating on its inner surface at least.At least the strength ratio I that is measured by EPMA on the inner surface of battery case
Fe/NiBe 0-0.1, i.e. 0＜I
Fe/Ni≤ 0.1.
According to this structure, in at least a portion inner surface of battery case, the exposure of Fe is minimized, thereby can make the formation of the oxide coating that causes due to the dissolving from the Fe of Fe exposed region, increase and the forming of local cell of the internal resistance that caused by this oxide coating minimize.Therefore, can realize electrochemical appliance with respect to the anti-leakage of conventional apparatus and storage characteristics excellence.
Another aspect of the present invention provides a kind of electrochemical appliance, and it comprises: the positive pole that comprises the positive electrode active materials in the mixture that is selected from hydroxy nickel oxide, manganese dioxide and hydroxy nickel oxide and manganese dioxide; Comprise the zinc component as the negative pole of negative active core-shell material; Be inserted in the barrier film between positive pole and negative pole; Alkaline electrolyte; And the battery case that holds positive pole, negative pole, barrier film and alkaline electrolyte.Battery case is comprised of the nickel-clad steel plate that has nickel coating on its inner surface at least.At least the strength ratio I that is measured by EPMA on the inner surface of battery case
Fe/NiZone greater than 1.0 and the ratio in whole zone (namely having rate) are 0-1.0%, i.e. 0＜(having rate)≤1.0%.
According to this structure, in at least a portion inner surface of battery case, the part of Fe is exposed minimize, thereby can make the formation of the oxide coating that causes due to the dissolving from the Fe of Fe exposed region, increase and the forming of local cell of the internal resistance that caused by this oxide coating minimize.Therefore, can realize electrochemical appliance with respect to the anti-leakage of conventional apparatus and storage characteristics excellence.
Another aspect of the present invention provides a kind of electrochemical appliance, and it comprises: the positive pole that comprises the positive electrode active materials in the mixture that is selected from hydroxy nickel oxide, manganese dioxide and hydroxy nickel oxide and manganese dioxide; Comprise the zinc component as the negative pole of negative active core-shell material; Be inserted in the barrier film between positive pole and negative pole; Alkaline electrolyte; And the battery case that holds positive pole, negative pole, barrier film and alkaline electrolyte.Battery case is comprised of the nickel-clad steel plate that has nickel coating on its inner surface at least.At least the strength ratio I that is measured by EPMA on the inner surface of battery case
Fe/NiBe 0-0.1 (0＜I
Fe/Ni≤ 0.1), and the strength ratio I that is measured by EPMA
Fe/NiZone greater than 1.0 and the ratio in whole zone (namely having rate) are 0-1.0%, i.e. 0＜(having rate)≤1.0%.
According to this structure, in at least a portion inner surface of battery case, can the exposure of Fe be minimized in more reliable mode, thereby can make the formation of the oxide coating that causes due to the dissolving from the Fe of Fe exposed region, increase and the forming of local cell of the internal resistance that caused by this oxide coating minimize.Therefore, can realize electrochemical appliance with respect to the anti-leakage of conventional apparatus and storage characteristics excellence.
Provided specially novel feature of the present invention in appending claims, can understand better and understand by reference to the accompanying drawings tissue of the present invention and content and other side and feature from following detailed specification.
Description of drawings
Fig. 1 is the cut-away section front view according to the alkaline primary battery of one aspect of the invention;
Fig. 2 means the stretching of manufacturing battery case and the figure of ironing step;
Fig. 3 means the figure of another step of the stretching of making battery case and ironing; And
Fig. 4 is the schematic sectional view by the battery case of stretching and ironing preparation.
Embodiment
With reference now to accompanying drawing,, explain the present invention.But the present invention is not limited to these embodiments.At first, the primary clustering of the alkaline battery in one aspect of the invention is described with reference to figure 1.Fig. 1 is the cut-away section front view of alkaline primary battery.
As shown in fig. 1, alkaline primary battery 100 of the present invention comprises: comprise the mixture that contains hydroxy nickel oxide, manganese dioxide and hydroxy nickel oxide and manganese dioxide as the positive pole 2 of the positive pole of positive electrode active materials; Comprise the zinc component as the gelling negative pole of negative active core-shell material; Be inserted in the barrier film 6 between positive pole 2 and negative pole 4; The alkaline electrolyte (not shown); And the battery case 8 that comprises positive pole 2, negative pole 4, barrier film 6 and alkaline electrolyte.
At first, battery case 8 is described.Battery case is formed by the nickel-clad steel plate with nickel coating.Nickel coating is positioned on the inner surface of battery case 8 at least.By conventional method for example stretch and ironing (drawing and ironing below is called D﹠amp; I processing) or stretch and prepare battery case 8, thus boost productivity and reduce the production cost of battery case.Adopt D﹠amp; I processing illustrates the method for preparing battery case 8 as an example.
According to D﹠amp; I processing, be prepared as follows battery case: arrange that a plurality of punch dies with different stretch/ironing (drawing/ironing) diameter reduce its ironing/ironing (ironing/ironing) diameter gradually, and by by what nickel-clad steel plate was made end cylinder being arranged with stamping head (die punch) extruding, make cylinder continuously by described a plurality of punch dies, thereby stretch and the ironing cylinder.With reference now to Fig. 2,3 and 4,, be described more specifically according to D﹠amp; An exemplary method of I processing preparation battery case 8.Fig. 2 and 3 shows D﹠amp; The figure of the step of I processing, and Fig. 4 is the schematic sectional view of gained battery case 8.
As shown in Fig. 2 and 3, by what above-mentioned nickel-clad steel plate was made end cylinder 24 arranged by using shaping mould (molding die) 20 and 22 processing of stamping head, thereby obtain battery case 8 with structure as shown in Figure 4.Shaping mould 20 is comprised of the ironing mould 20b-20d of a stretching die 20a and for example three arranged in series.As shown in Fig. 2 and 3, by with stamping head 22 extruded cylinder 24, make cylinder 24 continuously by mould 20a-20d, thereby stretching cylinder 24 once and three (D﹠amp of ironing; I processing).Mould 20a-20d has the structure that their inner diameter d a-dd reduces gradually.
Stamping head 22 has into shell part 22b, end section 22a and tapering part 22c.Be designed to shell part 22b and form bottom 8a and the first cylindrical side wall 8b of battery case 8 as shown in Figure 4, and design end section 22a forms the second cylindrical side wall 8c in Fig. 4.The diameter d of end section 22a
1With the diameter d that becomes shell part 22b
2Satisfy relation: d
1＜d
2In addition, for example by add nickel-clad steel plate in extruder, its plate that strikes out reservation shape and stretching and punching is prepared cylinder 24.Nickel-clad steel plate can be the steel plate (being that nickel-clad steel plate can have nickel coating on its one or both sides) that has plated nickel on its one or both sides.
The steel plate example that is used for preparing nickel-clad steel plate is the cold-rolled steel that mainly is fabricated from iron, and this also is applicable to other preparation method.
When using the battery case 8 preparation alkaline primary battery 100 that so obtains, the second cylindrical side wall 8c curves inwardly when sealing.In addition, bottom 8a and anodal 2 contact area less than with the contact area of the second cylindrical side wall 8c.Therefore, control the nickel coating (i.e. the madial wall of battery case 8 after the sealing) on the inner surface of the first cylindrical side wall 8b of battery case 8 at least, thereby one of satisfy in above-mentioned condition (1) and (2) at least.
Nickel coating on the inner surface of controlling the first cylindrical side wall 8b, can control on the inner surface of the second cylindrical side wall 8c and the nickel coating on the inner surface of bottom surface 8a, thereby one of satisfy in above-mentioned condition (1) and (2) at least.
That is, control the medial surface at least of the battery case 8 comprise nickel-clad steel plate, thus the strength ratio I that is measured by EPMA
Fe/NiBe 0-0.1 (condition (1)).In this scope, obtain particularly preferred anti-leakage characteristic and can suppress fully to store the reduction of rear low range flash-over characteristic.
In addition, strength ratio I
Fe/NiBe preferably 0.002-0.05.If it is 0.002 or larger, can reduces to a certain extent the amount of nickel plating and can reduce costs.If this ratio is 0.05 or less, after anti-leakage characteristic and storage, the low range flash-over characteristic is good and reduction that can suppress fully high-multiplying-power discharge performance.
In addition, strength ratio I
Fe/Ni0.002-0.005 more preferably.If it is 0.002 or larger, can reduces to a certain extent the amount of nickel plating and can reduce costs.If this ratio is 0.005 or less, after anti-leakage characteristic, storage, the rear high-multiplying-power discharge performance of low range flash-over characteristic and storage is good.Especially, if this ratio in described scope, can for example obtain good conductivity in more reliable mode between battery case 8 and anodal 2.Therefore, not needing provides the conductive layer that will be explained below to the inner surface of battery case 8, and can reduce preparation process and required assembly.Therefore, this scope is preferred.
In addition, the medial surface at least of the battery case 8 that comprises nickel-clad steel plate is controlled in the irrelevant or combination with it with condition (1), thus the strength ratio I that is measured by EPMA
Fe/Ni(be I greater than 1.0
Fe/NiThe rate that exists in zone＞1.0%) is 0-1.0% (condition 2).In this scope, obtain particularly preferred anti-leakage characteristic and can suppress fully to store the reduction of rear low range flash-over characteristic.
In addition, this exists rate to be preferably 0.01-0.7%.If it is 0.01% or larger, can reduces to a certain extent the amount of nickel plating and can reduce costs.If this ratio is 0.7% or less, obtain particularly preferred anti-leakage characteristic and store after the low range flash-over characteristic, and can suppress fully to store the reduction of rear high-multiplying-power discharge performance.
In addition, there is more preferably 0.01-0.3% of rate in this.If it is 0.01% or larger, can reduces to a certain extent the amount of nickel plating and can reduce costs.If this ratio is 0.3% or less, after anti-leakage characteristic, storage, the rear high-multiplying-power discharge performance of low range flash-over characteristic and storage is good.Especially, if this ratio in described scope, can for example obtain good conductivity in more reliable mode between battery case 8 and anodal 2.Therefore, not needing provides the conductive layer that will be explained below to the inner surface of battery case 8, and can reduce preparation process and required assembly.Therefore, this scope is preferred.
For example, by controlling plating step and/or the annealing steps in the nickel-clad steel plate preparation process, can obtain to comprise the satisfy condition battery case 8 of (1) and (2) nickel-clad steel plate one of at least of nickel coating.
As for the plating step, for example control at least one condition be selected from for example plating bath composition, plating bath temperature, plating bath pH and current density.Plating bath can be for example the plating bath that comprises nickelous sulfate, nickel chloride and boric acid, and can suitably control their concentration.
In addition, as for forming the annealing steps that carries out after coating, for example controlling at least one condition in annealing atmosphere composition, annealing temperature and annealing time that for example is selected from.Annealing atmosphere can be for example the gaseous mixture (reducing atmosphere) that comprises hydrogen and nitrogen, and can control the concentration of hydrogen and the flow velocity of gaseous mixture.
At least the nickel coating on the inner surface of battery case 8 first cylindrical side wall 8b (i.e. the inner surface of battery case 8 after annealing) preferably has the thickness of 0.2-1.0 μ m.If thickness is 0.2 μ m or larger, nickel coating can cover the whole inner surface of battery case 8 first cylindrical side wall 8b (i.e. the inner surface of battery case 8 after annealing) at least, thereby the exposure of Fe is minimized.Therefore, 0.2 μ m or larger thickness are preferred.If thickness is 1.0 μ m or less, suppressed the increase of coating amount, this is preferred aspect cost.
Stretching step and/or ironing step by in the plating step in the preparation process of control example such as nickel-clad steel plate and/or annealing steps and battery case 8 manufacture processes can be arranged on the thickness of nickel coating in above-mentioned scope.For example, reduced the original thickness of the nickel coating of nickel-clad steel plate by stretching step and/or ironing step, but in order to obtain to have the nickel-clad steel plate of predetermined thickness nickel coating, in advance the reduction degree of estimated thickness.
In the manufacture process of battery case 8, there is level of stretch difference in nickel coating between the first cylindrical side wall 8b on Fig. 4 arrow directions X and the second cylindrical side wall 8c.Therefore, the thickness of the upper nickel coating of the first cylindrical side wall 8b inner surface (i.e. the inner surface of battery case 8 after annealing) can have-error of 10-+10%.Can measure by fluorescent X-ray the thickness of the nickel coating of battery case 8.
The inner surface of battery case 8 can have the conductive layer (not shown), for example conductive carbon layer or equadag coating.In the case, can for example obtain good conductivity in battery case 8 inside between the inner surface of battery case 8 and anodal 2 in more reliable mode, thereby can suppress in more reliable mode the reduction of the storage characteristics that causes due to the internal resistance increase.But when one of should be understood that in above-mentioned condition (1) and (2) preferably are set at least, relatively traditional device is for realizing that good storage characteristics not necessarily always needs to form this conductive layer.For example, form this conductive layer by the dispersion liquid of spraying graphite in aqueous solvent on the inner surface of battery case 8.
Hydroxy nickel oxide can be traditional and can be by traditional method preparation.In addition, hydroxy nickel oxide can be for example to comprise for example solid solution of manganese (Mn), cobalt (Co) and calcium (Ca) of atom.In addition, the average nickel valence state of hydroxy nickel oxide is preferably 3.05 or larger, and more preferably 3.1 or larger.When using highly oxidized hydroxy nickel oxide, can significantly improve battery capacity.
Highly oxidized hydroxy nickel oxide easily prepares by the nickel hydroxide solid solution that chemical oxidation comprises manganese atom.When dissolving manganese in being used as the raw-material nickel hydroxide of hydroxy nickel oxide, the redox potential of nickel hydroxide reduces, thereby easily obtains highly oxidized hydroxy nickel oxide.Maximum for the density that makes hydroxy nickel oxide, the nickel hydroxide solid solution that comprises manganese atom preferably has β-type crystal structure.
In being used as the raw-material nickel hydroxide of hydroxy nickel oxide, the content of manganese is for example nickel and manganese total amount 1.0-7.0 % by mole, preferred 2.0-5.0 % by mole.If manganese content is 1.0 % by mole or larger, can obtain highly oxidized hydroxy nickel oxide in more reliable mode.If manganese content is 7.0 % by mole or less, the nickel ratio in nickel hydroxide can relative reduce, thereby can obtain satisfied battery capacity in more reliable mode.When using this nickel hydroxide as raw material, the manganese content in the gained hydroxy nickel oxide also becomes nickeliferous with the manganese total amount 1.0-7.0 % by mole of institute wherein.
Preferred hydroxy nickel oxide has the cobalt oxide that sticks on its particle surface.Has the hydroxy nickel oxide of cobalt oxide on particle surface from the ability raising of particle afflux, so further improved the particularly flash-over characteristic under heavy load.The amount of cobalt oxide is not more than 7.0 % by weight of hydroxy nickel oxide amount, and preferred 2.0-5.0 % by weight.If the amount of cobalt oxide is not more than 7.0 % by weight of hydroxy nickel oxide, the amount of cobalt oxide is not excessive.Therefore, for example can suppress cobalt is dissolved in electrolyte and the battery reliability can guarantee high-temperature storage in more reliable mode the time.In order further to improve the flash-over characteristic under heavy load, preferably use the amount of relative hydroxy nickel oxide to be the cobalt oxide of at least 2.0 % by weight.
Highly oxidized hydroxy nickel oxide has γ-type crystal structure, so it experiences large change in volume when battery discharge.In order to suppress the change in volume in this anodal 2, preferably use expanded graphite as the conductive agent that will be explained below.
The average grain diameter of the volume base of hydroxy nickel oxide is preferably 10-30 μ m.For example, when synthesizing the nickel hydroxide that is used as the primitive reaction thing by reactive crystallization, can control the particle diameter of hydroxy nickel oxide by the pH in the adjusting synthesising container, particle retention time, reaction temperature etc.In addition, even want to prepare large particle, averaging of income particle diameter (based on volume) can not surpass 30 μ m in many cases.In the density that improves cathode mix and improve aspect moldability the preferred hydroxy nickel oxide that obtains from the nickel hydroxide with large particle diameter that uses.From these aspects, the average grain diameter of the volume base of hydroxy nickel oxide is preferably 10-30 μ m.
Manganese dioxide can be traditional manganese dioxide and can prepare by traditional method.Particularly electrolytic manganese dioxide has high purity and therefore preferred use.For example, remove the sulfuric acid component and prepare electrolytic manganese dioxide by the electrolyzed strong acid manganese sulfate and by using the alkali neutralisation treatment of using NaOH (NaOH).If this neutralisation treatment is not enough, the gained electrolytic manganese dioxide comprises remaining sulfuric acid component, and when making battery the inner surface of the possible local corrosion battery case 8 of this acid.Therefore, the preferred neutralisation treatment of fully implementing.
In neutralisation treatment, part sodium hydroxide remains on the surface of gained electrolytic manganese dioxide particle or in the duct.Therefore, can judge the degree of neutralisation treatment from residual Na amount.The residual Na that comprises in manganese dioxide is preferably 2,000-7,000ppm.If it is 2,000ppm or larger, the amount of residual sulphur acid constituents is little, and this shows has suitably completed neutralization.Therefore, can suppress in more reliable mode the inner surface of sour local corrosion battery case 8.In addition, if residual Na is 7,000ppm or lower, has suppressed single electrode potential and the active reduction of electrolytic manganese dioxide, and can obtain suitable discharge performance.
In addition, the residual Na that comprises in manganese dioxide more preferably 2,000-5,000ppm.If it is 2,000ppm or larger, the amount of residual sulphur acid constituents is little, and this shows has suitably completed neutralization.Therefore, can suppress in more reliable mode the inner surface of sour local corrosion battery case 8.In addition, if residual Na is 5,000ppm or lower, has suppressed single electrode potential and the active reduction of electrolytic manganese dioxide in more reliable mode, and can obtain suitable discharge performance.
In addition, the average grain diameter of the volume base of manganese dioxide is preferably 30-50 μ m.For example, by regulating the condition of the manganese dioxide that separates with electrode in broken electro-deposition, can control the particle diameter of manganese dioxide.Generally, when particle too hour, discharge capacity reduces, and when particle is too large, the reduction of high load capacity flash-over characteristic.In addition, large particle diameter is more suitable for forming the cathode mix sheet.Consider these points, the volume base average grain diameter of manganese dioxide is preferably 30-50 μ m.
Conductive agent can be traditional conductive agent, and example comprises graphite, carbon black and carbon fiber.Because graphite has good moldability in forming the cathode mix sheet, it is preferred using graphite.Wherein, expanded graphite is preferred, because equal common graphite for example the high electronic conductivity of native graphite except having, it also has the ability of the stress in good compressibility (cushioning effect) and good mitigation cathode mix.Expanded graphite prepares with expanded graphite or graphite linings by the graphite with heat treatment well-crystallizeds such as sulfuric acid, nitric acid usually.
Binding agent can be traditional binding agent, and an example is polyethylene powders.In addition, as for various additives, can use for example surfactant of traditional additive.The back will illustrate operable alkaline electrolyte.
Be prepared as follows by above-mentioned and consist of the positive pole 2 that component forms.At first, make positive electrode active materials in the mixture that is selected from hydroxy nickel oxide, manganese dioxide or hydroxy nickel oxide and manganese dioxide and conductive agent for example graphite, a small amount of alkaline electrolyte, and binding agent as required and additive mix and stir.Under pressure, this granulate mixture is molded as hollow cylindrical, obtains the cathode mix sheet.A plurality of cathode mix sheets can be as anodal 2.
In addition, negative active core-shell material can be show low potential and can discharge and stable metal in alkaline aqueous solution.Negative pole 4 can comprise such metal, is added with another kind of metal or organic or inorganic additive in this metal and prevents corrosion and improve stability.
Alkaline electrolyte can be traditional alkaline electrolyte and the alkaline aqueous solution that preferably mainly is comprised of potassium hydroxide.Can also use NaOH, lithium hydroxide, calcium hydroxide etc.
Particularly preferably use and comprise the aqueous solution that is not less than 32 % by weight potassium hydroxide.As mentioned above, manganese dioxide (particularly electrolytic manganese dioxide) is acidic materials.Therefore, if the inner surface of battery case 8 has the zone that exposes Fe, Fe can be dissolved by manganese dioxide.But, if the concentration of potassium hydroxide aqueous solution is 32 % by weight or higher, can be with in more reliable mode and manganese dioxide and can suppress in more reliable mode the dissolving of Fe.
Next, illustrate that preparation comprises the method for the alkaline primary battery 100 of above-mentioned formation component.At first, will insert as anodal 2 the above-mentioned hollow cylindrical cathode mix of multi-disc sheet as in the battery case 8 of positive terminal.Push again electrode slice in battery case 8, make on its inner surface that closely is attached to battery case 8.
Subsequently, to the inner surface of the inner surface of anodal 2 hollow space and battery case 8 bottom surface 8a fixedly barrier film 6 and insulating lid 6a.Then, inject alkaline electrolyte, wetting barrier film 6 and anodal 2.Insulating lid 6a can be comprised of the material identical with barrier film 6.
After injecting alkaline electrolyte, the hollow space in barrier film 6 is packed into gelling negative pole 4.Subsequently, negative current collector 4a is inserted the middle part of gelling negative pole 4.Negative current collector 4a can be for example brass bar.Negative current collector 4a and resin-sealed parts 10 and integrated as the base plate 12 of negative terminals.
After this, the opening of battery case 8 (downside in Fig. 1) volume accompanies the edge of seal member 10 therebetween to the surrounding of base plate 12, thus the opening of sealed cell shell 8.At last, with the outer surface of outer label 4 clad battery shells 8, obtain alkaline primary battery 100.
Although just preferred embodiment has illustrated the present invention, be to be understood that the present invention is not limited to above-mentioned preferred embodiment.Therefore, various changes and modification are all possible.For example, in the preparation nickel-clad steel plate, can carry out annealing steps after producing battery case.In addition, can carry out plating step and annealing steps after using steel plate to produce battery case.
Embodiments of the invention hereinafter are described, but the present invention is not limited to these embodiment.
Embodiment 1
Approximately the manganese dioxide powder of 35 μ m (HHTF that can obtain from Tosho company or the NTA level that can obtain from Delta Electrical Industries Co., Ltd), hydroxy nickel oxide and powdered graphite form the first mixture to mix average grain diameters with the weight ratios of 50: 40: 10.Mix the potassium hydroxide aqueous solution of described the first mixture and 40 % by weight and fully stir with the weight ratios of 100: 1 and form the second mixture.The second mixture shaping mould is in blocks, then be broken into particle.Sieve particle with screen cloth, obtain the particle of 10-100 order size.Under pressure, these grain forming moulds are become hollow circular cylinder, obtain the cathode mix sheet.
Followingly can prepare hydroxy nickel oxide from the nickel hydroxide powder that Tanaka Chemical company obtains by chemical oxidation.The nickel hydroxide powder of average grain diameter 15 μ m is placed in sodium hydrate aqueous solution, and being then 12 % by weight with the effective dose concentration of q.s (corresponding to 2 equivalents), aqueous sodium hypochlorite solution mixes.Stir gained solution 3 hours, and prepared nickel oxyhydroxide powder.Then, water thoroughly washs powder and in a vacuum in 60 ℃ of dryings.Use in the present embodiment this powder.
In addition, with the weight ratio of 1: 33: 66 be mixed together Sodium Polyacrylate as gelling agent, as 40 % by weight potassium hydroxide aqueous solutions of alkaline electrolyte with as the zinc powder of negative active core-shell material, thereby form the gelling negative pole.Zinc powder used is the ABI35RAD (zinc-aluminium-bismuth-indium alloy) that can obtain from Mitsui Mining And Smelting Co., Ltd, and gelling agent is the PW-150 that can obtain from Ninon Junyaku Co., Ltd and the mixture of 1: 2 of the DK-500B that can obtain from Sanyo Chemical Industries Co., Ltd.
Next, preparation nickel-clad steel plate.This nickel-clad steel plate that is comprised of mild steel has the 1.5 thick nickel coatings of μ m on the surface of the inner surface that will become the bottomed cylindrical shape battery case, and has the 2.5 thick nickel coatings of μ m on the surface that will become the battery case outer surface.
Be prepared as follows nickel-clad steel plate.The cold-rolled steel sheet of the cranse form that at first, preparation 0.4mm is thick.This steel plate is mainly formed and is comprised the C of 0.028 % by weight, the Si of 0.01 % by weight, Mn, the S of 0.04 % by weight, the P of 0.013 % by weight and Al and the impurity of 0.04 % by weight of 0.18 % by weight by Fe.Electroplate this steel plate with nickel under condition as shown in table 1.
Table 1
Nickel-clad steel plate is put into continuous annealing furnace, and annealing 1 minute under 800 ℃ in the nitrogen stream (being reducing atmosphere) that comprises about 1% hydrogen is there spread Fe in nickel coating.Use the nickel-clad steel plate of gained, by the D﹠amp that has illustrated with regard to the embodiment of front; The I processing and manufacturing has the battery case of structure as shown in Figure 4.The thickness that has shown nickel coating on the battery case inner surface in table 2.
In addition, as for the inner surface of battery case, obtain the strength ratio I that is measured by EPMA
Fe/Ni(condition (1)) and strength ratio I
Fe/NiZone greater than 1.0 have a rate (condition (2)).More particularly, cut out approximately the sample of 1cm of 1cm * approximately from the inner surface of battery case.Then, sample is placed under electron probe microanalyzer and condition below and measures.
Analytical equipment: JEOL JXA-8900
Accelerating voltage: 15kV
The amount of electron beam (line): 0.05 μ A
Every point measurement time: 30ms
Every point measurement scope (1 pixel): 2 μ m
Every some range of exposures (probe diameter): 1 μ m or less
Specifically, at the lower characteristic X-ray of Fe and the characteristic X-ray of Ni measured of set point (zones of 2 μ m * 2 μ m), and based on the count value of characteristic X-ray, calculate the strength ratio I at this some place
Fe/NiIn measuring a sample, for example locate to carry out this measurement at 86700 points (255 point=86700, point * 340 point) in the area of 510 μ m * 680 μ m.Calculate all points strength ratio I
Fe/NiMean value, and use this mean value as strength ratio I
Fe/NiIn addition, the statistical analysis strength ratio I that obtains like this
Fe/NiObtain frequency distribution, and obtain strength ratio I
Fe/NiGreater than 1.0 count and all ratios of counting.Use this ratio as there being rate.Shown strength ratio I in table 2
Fe/NiAnd have rate.
Use the positive pole, negative pole and the battery case that so obtain, assembling has the alkaline primary battery of structure as shown in fig. 1.
At first, form the conductive layer of carbonaceous material on the inner surface of battery case 8.Then, insert a plurality of cathode mix sheets as positive pole in battery case, and push again them in battery case, make on its inner surface that closely is attached to battery case.The fixing bottomed cylindrical shape barrier film of being made by the adhesive-bonded fabric of vinal and rayon fiber and the plate-like insulating lid of being made by identical adhesive-bonded fabric on the inner surface of the hollow interior surface of positive pole and battery case bottom surface.Then, inject wherein the potassium hydroxide aqueous solution of 40 % by weight.
The graphite dispersing solution that mixes with liquid component by spraying on the inner surface of battery case 8 forms conductive layer.Remove liquid component by drying.Liquid component can be organic solvent or aqueous solvent.
The example of dispersion liquid has LB1000 (Timcal Ltd.), Eccocoate 257 (W.R.Grace ﹠amp; Co.); Electrodag 109 (Acheson Industries, Inc.); Electrodag 112, EB00, ED109B and EB020A (Acheson Industries, Inc.); And #27-5 and #523-3 (Nippon Graphite Industries, Ltd.).Suitable dispersion liquid is #523-3 or EB020A, because they are dispersion liquids of the graphite that mixes with water and are eco-friendly products.When using this aqueous solution type dispersion liquid and being indifferent to when forming rusty stain on inner surface at battery case (1) and the condition of can satisfying condition (2).Therefore, embodiment 1 uses #523-3 (Nippon Graphite Industries, Ltd.) as dispersion liquid.
After injecting alkaline electrolyte, the gelling negative pole is filled into hollow space in barrier film.Subsequently, the middle part that will insert the gelling negative pole with seal member and the integrated brass negative current collector of base plate.At last, with the surrounding of the opening of battery case volume to base plate, accompany the edge of seal member therebetween, thus the opening of sealed cell shell.With the outer surface of outer label clad battery shell, thereby prepare the alkaline primary battery of the present embodiment.
The present embodiment uses to have the 1.0 thick nickel coatings of μ m and have the nickel-clad steel plate of the thick nickel coating of 2.5 μ m on the surface that will become the battery case outer surface on the surface that will become the battery case inner surface.Thickness, strength ratio I except nickel coating on change battery case inner surface as shown in table 2
Fe/NiWith exist outside rate, use this nickel-clad steel plate, prepare alkaline primary battery according to method in the same manner as in Example 1.
Embodiment 3
The present embodiment uses to have the 0.5 thick nickel coating of μ m and have the nickel-clad steel plate of the thick nickel coating of 2.5 μ m on the surface that will become the battery case outer surface on the surface that will become the battery case inner surface.Thickness, strength ratio I except nickel coating on change battery case inner surface as shown in table 2
Fe/NiWith exist outside rate, use this nickel-clad steel plate, prepare alkaline primary battery according to method in the same manner as in Example 1.
Comparing embodiment 1
Thickness, strength ratio I except nickel coating on change battery case inner surface as shown in table 2
Fe/NiWith exist outside rate, prepare alkaline primary battery according to method in the same manner as in Example 1.
Comparing embodiment 2
Except after nickel-clad steel plate is processed into battery case, use additional nickel plating on the inner surface of battery case, the thickness of nickel coating on the battery case inner surface is changed into 1.5 μ m, and with strength ratio I
Fe/NiWith exist rate to change into outside 0, prepare alkaline primary battery according to method in the same manner as in Example 1.But, due to the plating step of replenishing, the time that the preparation of this alkaline primary battery need to be grown, and too thick nickel coating trends towards separating, and causes high cost.
[evaluation test]
(a) anti-leakage characteristic
In each of embodiment 1-3 and comparing embodiment 1 and 2, prepare 100 alkaline primary batteries.These 100 alkaline primary batteries were stored for 4 weeks in the environment of 60 ℃, and the quantity of counting leakage cell.Result is presented in table 2.
(b) gas flow that produces
In each of embodiment 1-3 and comparing embodiment 1 and 2, prepare 10 alkaline primary batteries.These 10 alkaline primary batteries were stored for 4 weeks in the environment of 60 ℃.Then, take and measure the gas flow of generation apart in water.Result is presented in table 2.
(c) storage characteristics
(i) low range flash-over characteristic
In each of embodiment 1-3 and comparing embodiment 1 and 2, prepare 10 alkaline primary batteries.These 10 alkaline primary batteries were stored for 4 weeks in the environment of 60 ℃.Then, make battery continuous discharge under the constant current of 100mA, and measuring voltage is down to the time that 0.9V spends.Result is presented in table 2.
(ii) high-multiplying-power discharge performance
In each of embodiment 1-3 and comparing embodiment 1 and 2, prepare 10 alkaline primary batteries.These 10 alkaline primary batteries were stored for 4 weeks in the environment of 60 ℃.Then, make battery continuous discharge under the constant current of 1500mA, and measuring voltage is down to the time that 0.9V spends.Result is presented in table 2.
Table 2 shows that alkaline primary battery according to an aspect of the present invention is being excellent aspect anti-leakage and storage characteristics.As mentioned above, the electrochemical appliance according to an aspect of the present invention of anti-leakage and storage characteristics excellence is not only applicable to alkaline primary battery, and be applicable to for example lithium primary battery of various electrochemical appliances, and respectively can be preferably as the electronic installation power supply of communication device and mancarried device for example.
Although with regard to the preferred embodiment of the invention, the present invention has been described, be to be understood that these disclosures should not be construed as restrictive.After disclosure on read, various changes and modification will undoubtedly become obvious for the those skilled in the art that the present invention relates to.Therefore, the plan appending claims is interpreted as covering institute and changes and revise, and treats as them and drops in true spirit of the present invention and scope.
Claims (8)
1. electrochemical appliance, it comprises:
The positive pole that comprises the positive electrode active materials in the mixture that is selected from hydroxy nickel oxide, manganese dioxide and hydroxy nickel oxide and manganese dioxide;
Comprise the zinc component as the negative pole of negative active core-shell material;
Be inserted in the barrier film between described positive pole and described negative pole;
Alkaline electrolyte; And
The battery case that holds described positive pole, described negative pole, described barrier film and described alkaline electrolyte,
Described battery case comprises the nickel-clad steel plate that has nickel coating on its inner surface at least, and
At least on the inner surface of described nickel-clad steel plate, by the Fe of electron probe microanalysis (EPMA) mensuration and the strength ratio I of Ni
Fe/NiZone greater than 1.0 and the ratio in whole zone are 1.0% or less.
2. according to claim 1 electrochemical appliance, the described inner surface of wherein said battery case also has conductive layer.
3. according to claim 1 electrochemical appliance, the strength ratio I of wherein said Fe and Ni
Fe/
NiZone greater than 1.0 and the ratio in whole zone are 0.01-0.7%.
4. according to claim 1 electrochemical appliance, the strength ratio I of wherein said Fe and Ni
Fe/
NiZone greater than 1.0 and the ratio in whole zone are 0.01-0.3%.
5. according to claim 1 electrochemical appliance, described in wherein said positive pole, manganese dioxide comprises the residual sodium of 2000 – 7000ppm.
6. according to claim 1 electrochemical appliance, described in wherein said positive pole, manganese dioxide comprises the residual sodium of 2000 – 5000ppm.
7. according to claim 1 electrochemical appliance, wherein said alkaline electrolyte is the aqueous solution that comprises more than or equal to the potassium hydroxide of 32 % by weight.
8. according to claim 1 electrochemical appliance, wherein said nickel coating has the thickness of 0.2-1.0 μ m.
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| US83327606P | 2006-07-26 | 2006-07-26 | |
| US60/833,276 | 2006-07-26 |
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| JP2011192559A (en) * | 2010-03-15 | 2011-09-29 | Fdk Energy Co Ltd | Battery can and alkaline battery |
| CN103337600B (en) * | 2013-05-18 | 2016-02-17 | 宁波倍特瑞能源科技有限公司 | A kind of alkaline dry battery positive pole housing and alkaline dry battery |
| CN103490071B (en) * | 2013-09-23 | 2015-08-19 | 哈尔滨工业大学（威海） | Lithium-Polyaniline Secondary Battery and preparation method thereof |
| EP3167503B1 (en) * | 2014-07-07 | 2019-09-04 | Patent Technology Trading Limited | Battery |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1082988A (en) * | 1992-06-22 | 1994-03-02 | 东洋钢钣株式会社 | Erosion-resisting Nickeled Steel Plate or steel bar and method for making thereof |
| CN1112737A (en) * | 1994-03-09 | 1995-11-29 | 电池技术公司 | High capacity rechargeable cell having manganese dioxide electrode |
| CN1311829A (en) * | 1998-07-24 | 2001-09-05 | 东洋钢钣株式会社 | Surface treated steel sheet for battery case, method for prodn. thereof, battery case formed by the steel sheet |
| CN1484714A (en) * | 2001-01-09 | 2004-03-24 | �ձ�������ʽ���� | Ni-plated steel plate for alkali-manganese dry cell anode can and alkali manganese dry cell anode can |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1052267C (en) * | 1996-03-21 | 2000-05-10 | 日本重化学工业株式会社 | Process of electrolytic manganese dioxide |
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2007
- 2007-06-21 JP JP2007163638A patent/JP2008034370A/en not_active Withdrawn
- 2007-07-26 CN CN2011100569324A patent/CN102163700B/en active Active
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1082988A (en) * | 1992-06-22 | 1994-03-02 | 东洋钢钣株式会社 | Erosion-resisting Nickeled Steel Plate or steel bar and method for making thereof |
| CN1112737A (en) * | 1994-03-09 | 1995-11-29 | 电池技术公司 | High capacity rechargeable cell having manganese dioxide electrode |
| CN1311829A (en) * | 1998-07-24 | 2001-09-05 | 东洋钢钣株式会社 | Surface treated steel sheet for battery case, method for prodn. thereof, battery case formed by the steel sheet |
| CN1484714A (en) * | 2001-01-09 | 2004-03-24 | �ձ�������ʽ���� | Ni-plated steel plate for alkali-manganese dry cell anode can and alkali manganese dry cell anode can |
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| CN101083337B (en) | 2011-04-27 |
| CN102163700A (en) | 2011-08-24 |
| CN101083337A (en) | 2007-12-05 |
| JP2008034370A (en) | 2008-02-14 |
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