CN101188292A - Sealed alkaline storage battery - Google Patents
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- CN101188292A CN101188292A CNA2007101698909A CN200710169890A CN101188292A CN 101188292 A CN101188292 A CN 101188292A CN A2007101698909 A CNA2007101698909 A CN A2007101698909A CN 200710169890 A CN200710169890 A CN 200710169890A CN 101188292 A CN101188292 A CN 101188292A
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Abstract
A sealed alkaline storage battery using, a positive electrode active material, as nickel oxyhydroxide including as an additive or coated with a rare earth element and/or a rare earth compound in a ratio measured based on the rare earth element of 0.05 through 5 wt%; and a sealed alkaline storage battery including, as a positive electrode active material, nickel oxyhydroxide having a half-width of a peak in a lattice plane in an X-ray diffraction pattern of 0.8 DEG or more. The pressure within the battery is not largely increased for a long period of charge-discharge cycles, and hence, the electrolyte hardly leaks.
Description
The application is dividing an application of No. 98802118.8 patent of invention submitting on January 12nd, 1998.
Technical field
The present invention relates to a kind of enclosed alkali storage battery, it comprises an active positive electrode material and a negative electrode active material, and they are contained in the battery case together, accounts for more than 75% of volume of battery case.More specifically say, the present invention relates to the improvement to a kind of active positive electrode material, so that a kind of enclosed alkali storage battery very reliably is provided, through charging-discharge cycles over a long time, electrolyte also is difficult to leak from storage battery.
Background technology
Proposed already, and in the enclosed alkali storage battery of Zn, adopted manganese dioxide as active positive electrode material (Japan special permission communique No 45-3570) as negative electrode active material.In addition, also propose, in the alkaline primary cell of Zn as negative electrode active material, the mixture that adopts nickel oxide and manganese dioxide is as active positive electrode material (day disclosure special permission communique No.49-114741).
Yet in charging-exoelectrical reaction, the invertibity of manganese dioxide is poor, recharges after the discharge to be difficult to make manganese dioxide to restore to the original state.Through the charging-discharge cycles of repeated multiple times, the effect of this active material reduces rapidly, thereby causes making the electric charge releasability to descend apace.In addition, the oxygen evolution ability of manganese dioxide is very low, so that between charge period,, increased the pressure in the battery because oxygen is emitted in the water decomposition on the positive electrode, the result, the connecting portion of battery case is bonding to be worse off, and electrolyte is leaked easily.
On the other hand, similar with the battery that adopts manganese dioxide, when using the mixture of nickel oxide and manganese dioxide in the storage battery that charges repeatedly and discharge (secondary cell), its oxygen evolution ability is too low, thereby battery in pressure raise easily, electrolyte is easily leaked.In addition, in charging-exoelectrical reaction, the invertibity of the manganese dioxide in the mixture is poor, thereby the charging-discharge cycles of process repeated multiple times, and the effect of this active material sharply reduces, and the result makes the electric charge releasability descend fast.
Above the weak point of two kinds of active positive electrode materials too many, can not be as the active positive electrode material of enclosed alkali storage battery.In the enclosed alkali storage battery that comprises a large amount of active materials, pressure rising during charging in the battery and the electrolyte leakage that produces therefrom are particularly evident.
Summary of the invention
Therefore, one of purpose of the present invention provides a kind of enclosed alkali storage battery that comprises a large amount of active materials with high reliability, the anxiety of electrolyte leakage of charging for a long time simultaneously-almost do not having again during discharge cycles.
Another object of the present invention provides a kind of like this enclosed alkali storage battery, and it not only in the initial stage of charge-discharge cycles but also when using for a long time, can both make active material keep good serviceability.
Enclosed alkali storage battery (second battery) according to second invention comprising: active positive electrode material NiOOH; By the negative electrode that negative electrode active material constitutes, it is a zinc electrode, cadmium electrode or hydrogenation hydrogen-absorbing alloy electrode, and active positive electrode material and negative electrode active material are contained in the battery case together, account for more than 75% of battery case volume.Have at least a rare earth element and/or at least a rare earth compound among the NiOOH as additive, the ratio of itself and NiOOH is 0.05 to 5 weight %.
Second invention is applicable to such as a kind of like this enclosed alkali battery that it adopts zinc, cadmium or hydrogenation hydrogen adsorbing alloy as negative electrode active material, needn't charge before using.
In addition, the enclosed alkali storage battery (the 3rd battery) according to the 3rd invention comprising: the active positive electrode material that NiOOH forms; By the negative electrode that negative electrode active material constitutes, it is zinc electrode, cadmium electrode or hydrogenation hydrogen-absorbing alloy electrode, and active positive electrode material and negative electrode active material are contained in the container together, account for more than 75% of battery volume.At least scribble a rare earth element and/or rare earth compound coating on the NiOOH particle surface, the ratio of itself and NiOOH is 0.05 to 5 weight %.
Second and the 3rd invention is applicable to a kind of like this enclosed alkali storage battery, and it comprises and account for the active material of battery case volume more than 75%, and active material all is contained in the battery case, and reason is as follows.Particularly be equipped with in battery case in the enclosed alkali battery of a large amount of active materials, in charging-discharge cycles repeatedly, the pressure in the battery increases easily, and electrolyte leaks easily.According to second and the 3rd invention, by the active positive electrode material that use has higher oxygen superpressure, the pressure that can suppress significantly in the battery raises.
In second battery, have at least a rare earth element and/or at least a rare earth compound among the NiOOH as additive, the ratio of rare earth element and NiOOH is 0.05 to 5 weight %.In the 3rd battery, scribble a rare earth element and/or rare earth compound coating on the NiOOH particle surface at least, the ratio of rare earth element and NiOOH is 0.05 to 5 weight %.When the ratiometer of pressing rare earth element and NiOOH as the quantity of the contained rare earth element of additive or coating and/or rare earth compound during less than 0.05 weight %, the oxygen superpressure of positive electrode can fully not increase, thereby the oxygen that can not suppress fully in the charging process discharges.On the other hand, when the content of additive or coating surpassed 5 weight %, the quantity as the NiOOH of active material of being packed into reduced, thereby has reduced discharge capability.
Described rare earth element is the generality term of following 17 kinds of elements: Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu.Rare earth compound is such as oxide being arranged, hydroxide, chloride and carbide.For increasing the oxidation superpressure of positive electrode, preferably adopt Y, Eu and Yb adopt Y compound, Er compound and Yb compound as rare earth compound as rare earth element.
When charging fully, be preferably 3.0 to 3.8 as the valence mumber of Ni among the NiOOH of active positive electrode material.If wherein the valence mumber of Ni is less than 3.0, then be difficult to the discharge capability that reaches sufficient.The valence mumber of Ni can not surpass 3.8 among the NiOOH.Charging continuously again after even battery charges fully, oxygen can only produce by the decomposition of water, and the valence mumber of Ni will never surpass 3.8.
For example, the oxidant that utilizes NaClO and so on can obtain NiOOH with the nickel hydroxide oxidation.
Have a kind of solid solution element among the NiOOH at least, be selected from Mn, Zn, Co, Bi and many rare earth elements.When use comprises above-mentioned any element as the NiOOH of solid solution element, can further increase the oxygen superpressure of positive electrode.The ratio of the solid solution element of NiOOH is preferably 5-50%, is defined by following formula:
The ratio of solid solution element (%)={ X/ (X+N) } * 100
Wherein X represents solid solution atoms of elements number contained among the NiOOH, and N represents the atomicity of Ni contained among the NiOOH.
If the ratio of solid solution element is too little, then can not increase the oxygen superpressure of positive electrode effectively.If the ratio of solid solution element is too big, the quantity that then is contained in to the hydroxide oxygen nickel in the constant volume reduces, and causes discharge capability to descend.
The coating that is formed on the 3rd battery for example can obtain like this: nickel hydroxide powder is added in the salting liquid of rare earth element, add sodium hydroxide solution and stir the pH value of regulating the solution that forms, solution was stirred 30 to 60 minutes, thereby utilize chemical method that rare earth element is separated out and on the particle surface of nickel hydroxide, form hydride.By changing concentration or its ratio of rare earth metal salt solutions, can regulate the thickness of coating with respect to the nickel hydroxide of powdered form.This coating can also be utilized the dry mixed mechanical loading method of powdered form hydroxide nickel and rare earth element and/or rare earth compound is formed.For example, in the non-oxide atmosphere inert gas is arranged, hydrogen, nitrogen and vacuum.The oxidation of hydroxide nickel can also be carried out after coating forms preceding or forms.
The rare earth element and/or the rare earth compound that comprise predetermined quantity in the positive electrode of the second or the 3rd battery, formation has higher oxygen superpressure.Therefore, the pressure in charging process in the battery does not have anything to increase, and through charging-discharge cycles for a long time, electrolyte also is difficult to leakage.
In addition, enclosed alkali storage battery (the 4th battery) according to the 4th invention comprising: the active positive electrode material that NiOOH forms, the negative electrode that constitutes by negative electrode active material, it is a zinc electrode, cadmium electrode or hydrogenation hydrogen-absorbing alloy electrode, active positive electrode material and negative electrode active material are contained in the container together, account for more than 75% of battery case volume.In the X-ray diffraction pattern, the half-breadth of NiOOH spike in crystal face (003) is more than 0.8 °.
The 4th invention is applicable to a kind of like this enclosed alkali storage battery, it comprises and accounts for the active material of battery case volume more than 75%, active material all is contained in the battery case, this is because be equipped with in its battery case in the enclosed alkali storage battery of a large amount of active materials, because the increase of the cell internal pressure that the reduction of the effectiveness of active material produces is an especially severe.
The degree of crystallinity of NiOOH is poor more, and the crystal face in the X-ray diffraction pattern (003) tip half-breadth is big more, and the tip is wide more.In the present invention, be the effect of enhanced activity material, active positive electrode material adopts such NiOOH, and its degree of crystallinity is relatively poor, and the half-breadth of the spike in crystal face (003) of X-ray diffraction pattern is more than 0.8 °.Herein, the half-breadth of spike refers to from the width of the tip of half eminence of baseline spike.
By discharge, NiOOH is become nickel hydroxide (Ni (OH)
2), by charging, with the Ni (OH) of discharge back generation
2Become NiOOH.When discharge, the proton (H that discharges among the NiOOH
+) enter in the electrolyte, and in charging process by Ni (OH)
2Absorb.Therefore, in order to make full use of NiOOH in charging-exoelectrical reaction, proton should be easy to move in NiOOH.It is relatively poor that proton can be easy to the degree of crystallinity of the NiOOH that moves therein.This be because, in NiOOH of the present invention, degree of crystallinity is relatively poor, it has half width in the crystal face (003) of the X-ray diffraction pattern more than 0.8 °.
For example, utilize the oxidant of NaClO and so on Ni (OH)
2Thereby oxidation obtains NiOOH.For example, by alkaline solution (as sodium hydroxide solution) and nickel salt solution (as nickel sulfate solution) are mixed the Ni (OH) that obtains precipitated form
2Make Ni (OH) by adjusting
2The pH value of the mixed liquor of precipitation can be adjusted Ni (OH)
2Degree of crystallinity.The pH value of mixed solution is low more, then formed Ni (OH)
2Degree of crystallinity poor more.Correspondingly, by with Ni (OH)
2The degree of crystallinity of the NiOOH that oxidation obtained is also relatively poor.
NiOOH can comprise and is selected from Bi, Cd, and Co, Mg, Mn, at least a element among Y and the Zn is as the solid solution element.If comprising, NiOOH then can suppress any in the above-mentioned element NiOOH and expand as the solid solution element.The ratio of solid solution element preferably 5 to 50% among the NiOOH.
If the ratio of solid solution element is too low, then can not suppresses NiOOH effectively and expand.If this ratio is too big, then the amount of the NiOOH that can pack into descends, the guiding discharge ability drop.
Because the active positive electrode material of the 4th battery uses NiOOH, its degree of crystallinity is poor, and at charging-interdischarge interval, proton is easy to move, so the effectiveness of active material can keep well in charging-discharge cycles over a long time.And because the effectiveness of active material can keep the long time well, the pressure between charge period in the battery seldom increases, thereby after the charging-discharge cycles, electrolyte also is difficult to leak for a long time.
Description of drawings
Fig. 1 is the partial sectional view of the Ni-Zn storage battery made by an embodiment;
Fig. 2 show the first time circulation time Mn ratio and the relation between the discharge capability;
Fig. 3 is the part of the X-ray diffraction pattern of NiOOH prepared among the embodiment, and its half width is 0.1 °.
Embodiment
On the basis of preferred embodiment, describe the present invention in detail below.Should be noted that the present invention is not limited to following embodiment, without departing from the present invention, can make suitable modification it.
(experiment 1)
In this experiment, for in enclosed alkali storage battery, adopting Zn as negative electrode active material, employing comprises the NiOOH of solid solution element M n, the mixture of manganese dioxide or nickel oxide and manganese dioxide has drawn the conservation rate and the quantity that the battery of leakage problem is arranged of battery capacity in various charging-discharge cycles as the situation of active positive electrode material.
(embodiment 1)
[preparation of positive electrode]
Is that the nickel sulfate solution of 0.1 mol and manganese sulfate solution that concentration is 0.1 mol mix in 4: 1 the ratio of atomic ratio of Ni and Mn with concentration.Then, the ammonia spirit of mixed solution that 100ml is made like this and the 5 weight % of 100ml injects the water of groove simultaneously, and the solution in the groove was mixed 1 hour under 35 ℃ temperature.Then, by the sodium hydroxide solution that drips 20 weight % solution in the groove is adjusted to pH11 and stirring simultaneously, again the solution that obtains was stirred 1 hour, utilize the pH value of the pH meter monitoring solution that has the auto thermal compensation function in the whipping process, thereby when the pH value descends slightly, drip the sodium hydrate aqueous solution of 20 weight %, make the pH value of solution always remain on 11 ± 0.3.As a result, the sediment that produces in the groove leaches, and the water flushing is also carried out vacuumize under room temperature (about 25 ℃).Thereby having obtained comprising the nickel hydroxide of solid solution element M n, the ratio of the atomicity sum of the atomicity of Mn and Mi and Ni is 20%.Can determine that from the X-ray diffraction of crystal structure this nickel hydroxide is α-Ni (OH)
2
Then, be that the sodium hydroxide solution of 10 mol and aqueous sodium hypochlorite solution that 500ml concentration is 10 weight % mix and stir with 500ml concentration, the solution that mixes is heated to 60 ℃, thereby forms the solution that carries out oxidation processes.Carry out in the solution of oxidation processes to 1000ml, add the above-mentioned nickel hydroxide that comprises solid solution element M n of 100g, the mixed liquor that forms was stirred one hour.Then, sediment is separated out, water washes, and is dry under 60 ℃ temperature, thereby obtains the NiOOH that comprises solid solution element M n as active positive electrode material.In the NiOOH that comprises solid solution element M n that obtains like this, absorb the atomicity that obtains Mn and Ni by atom, thereby calculate the ratio of Mn according to the number that is obtained.Found that the ratio of Mn is 20%.
Then, the potassium hydroxide aqueous solution 10g with the NiOOH powder 9g that comprises solid solution element M n that obtains like this and graphite powder 10g and 30 weight % mixed 30 minutes with blender.The matter utilization extrusion molding that forms is like this made the cylindricality positive electrode of hollow, and its external diameter is 1.3cm, and internal diameter is 0.85cm, highly is 1.15cm.When making battery, three such hollow cylindrical positive electrodes are serially connected successively as the cylindricality positive electrode of a hollow.
[preparation of negative electrode]
Potassium hydroxide aqueous solution with 65 parts of weight as the 40 weight % of the ZnO that comprises saturated quantity of the Zn powder of negative electrode active material and 34 parts of weight, and the acrylic resin of making gel of 1 part of weight (is made by Nihon Junyaku company, product code: polyacrylic acid 150) mix, thereby prepare the colloid negative electrode.
[manufacturing of first battery]
Above-mentioned positive electrode and negative electrode are used to make the Ni-Zn storage battery (first battery) of AA size, and it has so-called " type (inside-out type) from inside to outside " structure (positive electrode terminal is positioned on the battery case, and negative electrode terminal is positioned on the battery cap).Here, be a colloid negative electrode is arranged in the hollow space of hollow cylindrical positive electrode, and the dividing element of cylindrical membrane shape to be clipped between the two by the inside external form battery meaning.In order to control battery capacity by the capacity of positive electrode, the electrochemistry capacitance ratio of positive and negative electrode is set in 1: 2 (this Capacity Ratio is applicable to the battery that all experiments 1 to 4 are made).The total amount that is contained in the positive and negative electrode active material in the battery case occupies 80% of this vessel volume.(in addition, in all made below batteries, the total amount of positive and negative electrode active material also occupy its container volume 80%).
Fig. 1 is the partial sectional view of the Ni-Zn storage battery made like this.Ni-Zn storage battery shown in Figure 1 comprises: the cylindrical positive electrode container 1 (positive electrode outside terminal) that the end is arranged, negative electricity polar cap 2 (negative electrode outside terminal), insulation charges 3, cathodal current compiles element 4, it is by the brass manufacturing, the cylindricality positive electrode 5 of hollow (Ni electrode), columnar thin-film shape partition member 6, it is mainly made by vinylon, colloid negative electrode 7 (Zn electrode) etc.
(comparative example 1)
At first, be that concentration that the 1500ml liquor natrii hypochloritis of the 500ml nickel nitrate solution of 2 mol and 10 weight % is instilled into 2000ml is in the potassium hydroxide solution of 14 mol and mixes with it with concentration, the mixture that forms was slowly cooled off one hour.Then, formed sediment is separated out, and is the potassium hydroxide solution cleaning of 2 mol with concentration, the water flushing, and dry under 90 ℃ temperature.So just obtained being used for the nickel oxide powder of active positive electrode material.
Then, with the above-mentioned nickel oxide powder of 50g, the manganese dioxide powder of 30g, the powdered graphite of 15g and the polyvinyl resin of 5g mix.With this mixture and concentration is that the potassium hydroxide solution 20ml of 7 mol mixes, and formed material is made positive electrode with extrusion molding.
Except adopting this positive electrode, utilize with embodiment 1 identical method and make enclosed alkali storage battery X.
(comparative example 2)
With the manganese dioxide powder of 100g, the powdered graphite of 15g and the polyvinyl resin of 5g mix, and the concentration of formed mixture and 2ml is that the potassium hydroxide solution of 7 mol mixes.Formed material extrusion molding is made positive electrode.
Except employed positive electrode, according to making enclosed alkali battery Y with embodiment 1 identical mode.
[capability retention and the number of batteries that leakage in the charging-discharge cycles of each battery, occurs]
For only being the different above-mentioned three types sealed cell a of active positive electrode material, X, Y charges-discharge cycle test, earlier under the load of 3.9 Ω, make battery discharge to 0.9V, under each circulation, charge to 1.95V during in 150mA then, so obtained 5 times, 10 times, 25 times and the capability retention of every kind of battery of 50 circulation times and the number of the battery that generation is leaked.For every type battery, use 10 batteries to obtain the number of capability retention and generation leakage cell.The results are shown in table 1.The capability retention of each cycle-index of every kind of battery shown in Fig. 1 be battery the first time circulation time discharge capacity a percentage (%), it is the mean value of the capability retention of the battery that takes place of no electrolyte leakage.The molecule of " ratio of the battery that take place to leak " this mark down is corresponding to the number of the battery that the electrolyte leakage generation is arranged in the table 1.
Table 1
| Battery | Charge-discharge cycles | The ability conservation rate | The leakage cell ratio |
| a |
5 10 25 50 5 10 25 50 5 10 25 50 | 100 100 100 98 100 100 95 93 60 50 45 40 | 0/10 0/10 0/10 0/10 0/10 2/10 4/10 6/10 3/10 5/10 7/10 8/10 |
As shown in table 1, for enclosed alkali storage battery a (first battery), 25 times and 50 circulation times, capability retention are respectively up to 100 and 98, even under the situation of 50 circulations, the number of battery cells that the generation of leaking is arranged is zero.On the other hand, for enclosed alkali battery X (relatively battery), at 25 times and 50 circulation times, capability retention is respectively 95 and 93, just a little less than enclosed alkali battery a, but at 10 times, 25 times and 50 circulation times, the number of battery cells that takes place to leak is but respectively up to 2,4 and 6.For enclosed alkali battery Y (relatively battery), at 5 times, 10 times, 25 times and 50 circulation times, capability retention are low respectively to reach 60,50,45 and 40, and the number of battery that leakage takes place is respectively up to 3,5,7 and 8.
(experiment 2)
In this experiment, the relation between γ ratio and the leakage is studied.
With concentration be 10 mol the 500ml sodium hydroxide solution respectively and 100ml, 200ml, 300ml, the liquor natrii hypochloritis of the 10 weight % of 400ml mix and stir simultaneously, and are heated to 60 ℃, prepare oxidation treatment liquid.According to producing enclosed alkali storage battery A with embodiment 1 identical mode, B, C, D, difference only is that used oxidation treatment liquid has nothing in common with each other.With experiment 1 identical condition under to enclosed alkali storage battery A, B, C and D charge-the discharge cycles experiment, thereby have drawn at 5 times, 10 times, the number of the battery of leakages takes place in 25 times and 50 circulation times.The results are shown in table 2.In the table 2, the result of enclosed alkali storage battery a comes from table 1.
Table 2
| Battery | The γ ratio | The 5th circulation | The 10th circulation | The 25th circulation | The 50th circulation |
| A B C D a | 46 65 87 90 100 | 0/10 0/10 0/10 0/10 0/10 | 1/10 0/10 0/10 0/10 0/10 | 2/10 1/10 1/10 0/10 0/10 | 4/10 2/10 1/10 0/10 0/10 |
As shown in table 2, for enclosed alkali storage battery B, C, D and a (first battery), 10 circulation times, the number that the battery of leakage takes place is 0, and for enclosed alkali storage battery A (comparative example), this number is 1.This fact shows that must adopt the NiOOH and its γ ratio that comprise solid solution element M n is more than 65%, so that obtain the high reliability enclosed alkali storage battery that about 10 circulation times do not leak.For enclosed alkali storage battery D and a, even 50 circulations, the cell number that takes place to leak also is zero.This fact shows, is the enclosed alkali storage battery that acquisition has high reliability, and preferably the γ ratio is more than 90%.The γ ratio is low more, and promptly β-NiOOH shared ratio in NiOOH is big more, the easy more leakage of electrolyte, and this is because when the shared ratio of β-NiOOH is very big, even interpolation solid solution Mn, the oxygen superpressure can not increase greatly yet.
(experiment 3)
In this experiment, to the first time circulation time Mn ratio and the ratio of relation between the discharge capability and Mn study with the relation between the leakage.
[ratio of circulation time Mn and the relation between the discharge capability for the first time]
Prepare NiOOH according to the mode identical with first embodiment, the ratio of the solid solution element M n that it comprises is respectively 0%, 2%, 5%, 10%, 40%, 50%, 55% and 60%, different is, for obtaining to comprise the nickel hydroxide of solid solution element M n, changed the mixing ratio between nickel sulfate solution and the manganese sulfate solution.As a result, utilize the NiOOH that comprises solid solution element M n, produce enclosed alkali storage battery E respectively, F, G, H, I, J, K and L as active positive electrode material.For obtaining the discharge capability of the 1st circulation time, make above-mentioned each battery under the load of 3.9 Ω, be discharged to 0.9V.The results are shown in Fig. 2.Figure 2 illustrates the 1st discharge capability (ratio of its Mn is 20%) of enclosed alkali battery a.Fig. 2 is as the ratio of the Mn of the NiOOH of solid solution element and the curve of the 1st circulation time discharge capability with Mn, wherein ordinate is represented the discharge capability of the 1st circulation, abscissa is represented the ratio of Mn, and wherein resulting this index of discharge capability by the 1st time represented circulation time of ordinate is that the discharge capability with hypothesis enclosed alkali storage battery a is 100 to do the basis.
As shown in Figure 2, compare with a to J at the enclosed alkali storage battery E below 50% with the ratio of Mn, the ratio of Mn is very little at the discharge capability of the 1st circulation time at 55% and 60% enclosed alkali storage battery K and L.This is because if the ratio of Mn is too high, can not be dissolved among the NiOOH fully as the Mn of solid solution element, thereby the free oxidation manganese that is produced can stop discharge.This fact shows that the ratio of Mn is preferably in below 50%.
[relation between the ratio of Mn and the leakage]
With experiment 1 identical condition under, the enclosed alkali storage battery E that initial discharge capacity is very sufficient, F, G, H, I and J charge-discharge cycle test, thereby draw at 5 times, 10 times, the number of the battery of 25 times and 50 times circulation time generation leakages the results are shown in table 3.The result of enclosed alkali storage battery a is identical with table 1 in the table 3.
Table 3
| Battery | The Mn ratio | The 5th circulation | The 10th circulation | The 25th circulation | The 50th circulation |
| J I a |
50 40 20 10 5 2 0 | 0/10 0/10 0/10 0/10 0/10 0/10 0/10 | 0/10 0/10 0/10 0/10 0/10 0/10 1/10 | 0/10 0/10 0/10 0/10 0/10 1/10 1/10 | 0/10 0/10 0/10 0/10 0/10 1/10 2/10 |
As can be understood from Table 3, by add solid solution element M n in NiOOH, electrolyte is more difficult to be leaked.For the ratio of Mn is 5% enclosed alkali storage battery B, and the number of battery cells that 50 circulation times take place to leak is 0, and is 2% storage battery F for the ratio of Mn, at 25 circulation time generation electrolyte leakages.This fact shows, for the enclosed alkali battery of the high reliability that obtains not have to leak through long-term charging-discharge cycles, and the ratio of Mn preferably 5%.
Consider the ratio of Mn and for the first time ratio of the relation of circulation time discharge capability and Mn and the relation between the battery that takes place to leak, active positive electrode material preferably adopts such NiOOH that comprises solid solution element M n, and wherein the ratio of Mn is 5 to 50%.
(experiment 4)
In this experiment, adopt NiOOH that contains solid solution element M n and the α-Ni (OH) that comprises solid solution element M n
2Mixture as active positive electrode material, to α-Ni (OH)
2The permission mixing ratio analyze.
With different ratio wherein the ratio of Mn be α-Ni (OH) of 20%
2With the γ ratio be 65%, mix the preparation active positive electrode material thereby the ratio of Mn is 20% NiOOH, they are to obtain when the positive electrode of preparation embodiment 1.
In addition, with the Zn powder of 55 parts of weight, the Zinc oxide powder of 10 parts of weight, the potassium hydroxide aqueous solution of the 40 weight % of the Zn that comprises saturated quantity of 34 parts of weight and mix as the acrylic resin of 1 part of weight of gel, thus obtain the colloid negative electrode.According to making enclosed alkali storage battery M with embodiment 1 identical mode, N, O, P and Q, difference is that it adopts active positive electrode material recited above and negative electrode active material.Each battery is charged-discharge cycle test, in circulation each time, when 150mA, it is charged to 1.95V, and under the load of 3.9 Ω, it is discharged to the cell voltage of 0.9V, thereby 5 times have been obtained, 10 times, 25 times, the number of the battery of leakage takes place in 50 circulation times.The results are shown in the table 4.
Table 4
| Battery | The ratio (weight %) that contains the NiOOH of solid solution element M n | The 5th circulation | The 10th circulation | The 25th circulation | The |
| M N O P Q | |||||
| 50 60 70 90 100 | 1/10 0/10 0/10 0/10 0/10 | 1/10 0/10 0/10 0/10 0/10 | 1/10 0/10 0/10 0/10 0/10 | 3/10 1/10 0/10 0/10 0/10 |
As can be seen from Table 4, the NiOOH and the α-Ni (OH) that comprises solid solution element M n that comprise solid solution element M n
2Mixture can be used as active positive electrode material, when using this mixture, comprise α-Ni (OH) of solid solution element M n
2Mixing ratio be below the 40 weight %.
(experiment 5)
In this experiment, the second battery A1 to A21 that comprises the NiOOH of rare earth element or rare earth compound with respect to employing, adopt and comprise that neither rare earth element does not comprise the comparison battery C1 of the NiOOH of rare earth compound yet, adopt the comparison battery C2 of manganese dioxide as active positive electrode material, adopt the comparison battery C3 of the mixture of nickel oxide and manganese dioxide as active positive electrode material, drawn at 5 times, 10 times, 25 times, the capability retention of 50 times and 75 times circulation times and the number of battery cells of not leaking.
(the second battery A1 to A21)
[preparation of positive electrode]
The concentration of 500ml is 1 liter of the aqueous sodium hypochlorite solution mixed solution of the 10 weight % of the sodium hydrate aqueous solution of 10 mol and 500ml, is heated to 60 °, and with the Ni (OH) of 100g
2Powder adds, and stirs simultaneously.After the liquid mixing and stirring 1 hour, leach sediment, water cleans, and dry under 60 ℃ temperature, thereby obtains NiOOH.
With mixing arrangement by following mixed 30 minutes: the NiOOH that obtains above (active positive electrode material) of 100 parts of weight; The Y of 1 part of weight, Sc, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Mm (mixture of various rare earth elements, mishmetal) or the displacement measuring and calculating of pressing rare earth element, the Y of 1 part of weight
2O
3, YF
3Or Y
2(CO
3)
3The graphite of 10 parts of weight; The potassium hydroxide solution of 30 weight % of 10 parts of weight.Formed mixture is carried out extrusion molding, make it to become the cylindrical positive electrode of hollow, its external diameter is 1.3cm, and internal diameter 0.85cm highly is 1.15cm.In this way, the ratio according to rare earth element and NiOOH1 weight % adds every kind of rare earth compound among the NiOOH.As for Mm, the employed La that comprises, Ce, the ratio of the atom of the mixture of Pr and Nd are 45: 30: 15: 10.When making each battery, three such hollow cylindrical positive electrodes are serially connected forms the cylindrical positive electrode of a hollow.
[preparation of negative electrode]
The colloid negative electrode is preparation like this, zinc powder with 65 parts of weight, the potassium hydroxide solution of the ZnO that comprises 6 weight % (saturation capacity) of 40 weight % of 34 parts of weight, the acrylic resin that is used as 1 part of weight of colloidal substance (is used Nihon Junyaku company, product code: polyacrylic acid 150) mix.
[manufacturing of battery]
Except adopting above-mentioned positive electrode and negative electrode respectively, according to making the Ni-Zn storage battery A1 to A21 (second battery) of AA size with experiment 1 embodiment 1 identical mode.
(relatively battery C1)
Except do not add any rare earth element or rare earth compound in NiOOH when making positive electrode, relatively the manufacture of battery C1 is identical with the second battery A1 to A21.
(relatively battery C2)
The concentration that in concentration is the 2000ml potassium hydroxide solution of 14 mol, splashes into 500ml be the nickel nitrate solution of 2 mol and 1500ml 10 weight % the liquor natrii hypochloritis and mix, formed mixed liquor cooled off 1 hour gradually.Then, leaching the sediment of formation, is the potassium hydroxide solution cleaning of 2 mol with concentration, and water cleans, and dry under 90 ℃ temperature.Thereby obtained being used for the nickel oxide powder of active positive electrode material.
With the above-mentioned nickel oxide powder of 50g, the 30g manganese dioxide powder, 15g powdered graphite and 5g polyvinyl resin mix, and are that the potassium hydroxide solution 20ml of 7 mol further mixes with concentration.With the mixture extrusion molding that forms is the cylindrical positive electrode of hollow.
Except positive electrode, use the mode identical to make comparison battery C2 with the second battery A1 to A21.
(relatively battery C3)
With the 100g manganese dioxide powder, 15g powdered graphite and 5g polyethylene resin powder are mixed, and and concentration be that the potassium hydroxide solution 20ml of 7 mol further mixes.The mixture extrusion molding that forms is made it to become the cylindrical positive electrode of hollow.
Except positive electrode, relatively the manufacture of battery C3 is identical with the second battery A1 to A21.[capability retention of each battery under different charging-discharge times and the number of battery cells that leakage takes place]
With experiment 1 identical condition under each battery is charged-discharge cycle test, thereby obtain 5 times, 10 times, 25 times, 50 times, the number of the battery that the capability retention of 75 times and 100 times circulation times and taking place leaks.For obtaining the number of capability retention and the battery that takes place to leak, to 10 batteries of battery employing of each type.The results are shown in table 5 in 8.Capability retention under each charging-discharge cycles shown in the table is expressed as the percentage of the discharge capacity of circulation time for the first time, and it is the mean value of the capability retention of the battery that do not take place to leak.And, be listed in the number of the molecule of the mark in " ratio that the battery of leakage takes place " corresponding to the battery that electrolyte leakage is arranged.
Table 5
| Electricity ground | Charge-discharge cycles | Ability conservation rate (%) | The leakage cell ratio |
| A1 (containing Y) A2 (containing Sc) A3 (containing La) A4 (containing Ce) A5 (containing Pr) A6 (containing Nd) | 5 10 25 50 75 100 5 10 25 50 75 100 5 10 25 50 75 100 5 10 25 50 75 100 5 10 25 50 75 100 5 10 25 50 75 100 | 100 100 100 100 100 100 100 100 100 100 99 96 100 100 100 100 100 98 100 100 100 100 99 97 100 100 100 100 100 99 100 100 100 100 100 98 | 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 1/10 0/10 0/10 0/10 0/10 0/10 1/10 0/10 0/10 0/10 0/10 1/10 1/10 0/10 0/10 0/10 0/10 0/10 1/10 0/10 0/10 0/10 0/10 0/10 1/10 |
Table 6
| Battery | Charge-discharge cycles | Ability conservation rate (%) | The leakage cell ratio |
| A7 (containing Pm) A8 (containing Sm) A9 (containing Eu) A10 (containing Gd) A11 (containing Tb) A12 (containing Dy) | 5 10 25 50 75 100 5 10 25 50 75 100 5 10 25 50 75 100 5 10 25 50 75 100 5 10 25 50 75 100 5 10 25 50 75 100 | 100 100 100 100 99 97 100 100 100 100 100 98 100 100 100 100 99 98 100 100 100 100 99 97 100 100 100 97 96 94 100 100 100 95 93 91 | 0/10 0/10 0/10 0/10 1/10 2/10 0/10 0/10 0/10 0/10 0/10 1/10 0/10 0/10 0/10 0/10 1/10 2/10 0/10 0/10 0/10 0/10 0/10 1/10 0/10 0/10 0/10 1/10 2/10 2/10 0/10 0/10 0/10 2/10 3/10 3/10 |
Table 7
| Battery | Charge-discharge cycles | Ability conservation rate (%) | The leakage cell ratio |
| A13 (containing Ho) A14 (containing Er) A15 (containing Tm) A16 (containing Yb) A17 (containing Lu) A18 (containing Mm) | 5 10 25 50 75 100 5 10 25 50 75 100 5 10 25 50 75 100 5 10 25 50 75 100 5 10 25 50 75 100 5 10 25 50 75 100 | 100 100 100 99 96 95 100 100 100 100 100 100 100 100 100 99 98 94 100 100 100 100 100 100 100 100 100 98 96 94 100 100 100 100 100 98 | 0/10 0/10 0/10 1/10 2/10 3/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 1/10 3/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 1/10 2/10 3/10 0/10 0/10 0/10 0/10 0/10 1/10 |
Table 8
| Battery | Charge-discharge cycles | Ability conservation rate (%) | The leakage cell ratio |
| A19 (contains Y 2O 3) A20 (contains YF 3) A21 (contains Y 2(CO 3) 3) | 5 10 25 50 75 100 5 10 25 50 75 100 5 10 25 50 75 100 | 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 | 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 |
| |
5 10 25 50 75 100 5 10 25 50 75 100 5 10 25 50 75 100 | 100 100 98 95 89 85 100 100 95 93 87 79 60 55 50 45 40 35 | 0/10 0/10 0/10 0/10 2/10 5/10 0/10 2/10 4/10 6/10 8/10 9/10 3/10 3/10 5/10 7/10 8/10 9/10 |
Be appreciated that from table 5 to table 8 with battery C1 to C3 relatively and compare that the second battery A1 to A21 has higher capability retention, charging-discharge cycles is more difficult for a long time leaks.(experiment 6)
In this experiment, the quantity of adding the Y among the NiOOH to and the relation between discharge capability and the leakage are analyzed.
Enclosed alkali storage battery a1, a2, a3, a4, a5, a6, a7, the manufacture of a8 and a9 is identical with the second battery A1, just the addition difference of Y, be respectively 0.01 part of weight, 0.05 part of weight, 0.1 part of weight, 0.5 part weight, 2 parts of weight, 3 parts of weight, 5 parts of weight, 6 parts or 7 parts of weight are based on 100 parts of NiOOH.The ratio of pressing Y and NiOOH calculates, and the content of Y is respectively 0.01,0.05 among the battery a1 to a9,0.1,0.5,2,3,5,6 and 7 weight %.With experiment 1 identical condition under each battery a1 to a9 is made charging-discharge cycle test, thereby draw at the discharge capability of the 1st circulation time and at the discharge capability of the 100th circulation time and the number of the battery of leakage takes place.The results are shown in the table 9.Also show the second battery A1 in the table 9 at the discharge capability of the 1st circulation time and at the discharge capability of the 100th circulation time and the number of the battery that leaks takes place.The discharge capability of the 1st time shown in the table 9 and 100 circulation times be the supposition second battery the first time circulation time discharge capability be the index that was drawn in 100 o'clock.
Table 9
| Battery | Y content (weight %) | The discharge capability of the 1st circulation time | The discharge capability of the 100th circulation time | The leakage cell ratio |
| a1 a2 a3 a4 A1 a5 a6 a7 a8 a9 | 0.01 0.05 0.1 0.5 1 2 3 5 6 7 | 101 101 101 100 100 99 98 96 86 82 | 86 92 95 100 100 99 98 96 86 82 | 4/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 |
As can be understood from Table 9, for the battery that makes acquisition has bigger discharge capability and is difficult to leak, the quantity of adding the Y among the NiOOH to should be 0.05 to 5 weight %.Confirmed that also when using rare earth element or rare earth compound, the quantity (by the conversion of the rare earth element in the rare earth compound) of adding among the NiOOH should be 0.05 to 5 weight %.Battery a1 is very little at the discharge capability of 100 circulation times, and this is because the amount of the Y that is added is very little, so that the oxygen superpressure can not fully increase, makes γ-NiOOH become β-NiOOH, thereby has reduced the number of reaction electronics.
(experiment 7)
In this experiment, the valence mumber of Ni among the NiOOH and the relation between discharge capability and the leakage are analyzed.
Enclosed alkali storage battery a10, a11, the manufacture of a12 and a13 is identical with the second battery A1, and the amount of just sneaking into the clorox of 10 weight % in the sodium hydroxide solution of 500ml is 100,200,300 or 1000ml, rather than 500ml.With experiment 1 identical condition under every kind of battery is charged-discharge cycle test, thereby obtain the number of the battery that the generation of the discharge capacity of circulation time for the first time and the 100th circulation time leaks.The results are shown in the table 10.Table 10 also shows discharge capability and the discharge capability of 100th circulation time and the number of battery that generation leak of the second battery A1 at the 1st circulation time.Discharge capability shown in the table 10 be the supposition second battery the first time circulation time discharge capability be the index that was drawn in 100 o'clock.
Table 10
| Battery | The valence mumber of Ni | The battery ability | The leakage cell ratio |
| a10 a11 a12 A1 a13 | 2.6 2.8 3.0 3.5 3.8 | 30 70 98 100 110 | 0/10 0/10 0/10 0/10 0/10 |
As can be seen from Table 10, for obtaining to have the battery of bigger discharge capability, the valence mumber that preferably adopts Ni is that 3.0 to 3.8 NiOOH is as active positive electrode material.
(experiment 8)
In this experiment, for the 3rd battery B1 to B17, they use NiOOH, scribble rare earth element or rare earth compound on its particle surface, drawn at 5 times, and 10 times, 25 times, 50 times, the number of battery cells and the capability retention of 75 times and 100 times circulation time generation leakages.
(the 3rd battery B1 to B17)
Xiang Shuizhong dissolves in the Y of 3.43g
2(SO
4)
38H
2O, the Sc (NO of 6.73g
3)
34H
2O, the La (NO of 3.12g
3)
36H
2O, the Ce (NO of 3.10g
3)
36H
2O, the Pr (NO of 3.09g
3)
36H
2O, the Nd (NO of 3.04g
3)
36H
2O, the Pm (NO of 3.03g
3)
36H
2O, the Sm (NO of 2.95g
3)
36H
2O, the Eu (NO of 2.93g
3)
36H
2O, the Gd (NO of 2.75g
3)
35H
2O, the Tb (NO of 2.74g
3)
35H
2O, the Dy (NO of 2.70g
3)
35H
2O, the Ho (NO of 2.67g
3)
35H
2O, the Er (NO of 2.65g
3)
35H
2O, the Tm (NO of 2.63g
3)
35H
2O, the Yb (NO of 2.39g
3)
33H
2Lu (the NO of O and 2.37g
3)
33H
2O, and make 1 liter the aqueous solution.The solid solution pellet powder that adds 100g in each solution promptly comprises the nickel hydroxide of the solid solution element M n of 20 weight %.In resulting solution, add sodium hydrate aqueous solution and stirring that concentration is 1 mol, thereby the pH value of gained solution is transferred to 11, solution was stirred one hour.In whipping process, utilize the pH meter monitoring pH value of band temperature compensation function, thereby when the pH value slightly reduces, be that the sodium hydrate aqueous solution of 1 mol makes the pH total amount roughly remain on 11 by adding concentration.Leach sediment subsequently, water cleans and is dry, thereby prepares the composite particles powder, and wherein, the rare earth element coating is formed on the particle surface of nickel hydroxide.In all powder, the ratio of rare earth element (coating) and nickel hydroxide (former particle) is 1 weight %.
Then, be that the sodium hydroxide solution 500ml of 10 mol and mixture that concentration is the liquor natrii hypochloritis 500ml of 10 weight % are heated to 60 ℃ with concentration, and add the composite particles powder of 100g, stir simultaneously.Resulting solution was stirred one hour, leaches sediment, water clean and in the time of 60 ℃ drying, thereby prepare the composite particles powder, wherein, on the particle surface of NiOOH, form the rare earth element coating.In all powder, the ratio of rare earth element (coating) and NiOOH (former particle) is roughly 1 weight %.
This composite particles powder with 100 parts of weight, the potassium hydroxide aqueous solution of 30 weight % of the graphite of 10 parts of weight and 10 parts of weight stirred 30 minutes with blender, with formed material extrusion molding is the cylindrical positive electrode of hollow, its external diameter is 1.3cm, internal diameter is 0.85cm, highly is 1.15cm.When making each battery, three this hollow circuit cylinder positive electrodes are connected in series hollow cylindrical positive electrode of formation.
Thereafter, except adopting above-mentioned positive electrode, the method for making the 3rd battery B1 to B17 is identical with the second battery A1 to A21.
[number of the battery that the capability retention of each battery under different chargings-discharge cycles number of times and generation are leaked]
With experiment 1 identical condition under, each battery is charged-discharge cycle test, thereby draws 5 times, 10 times, 25 times, 50 times, 75 times and 100 circulations down capability retention and the number of battery cells of leakage takes place.Battery to every kind of model adopts 10 batteries, with the number of battery cells that obtains capability retention and take place to leak.The results are shown in table 11 to 13.Listed capability retention shows work with respect to the battery ratio of the discharge capability of circulation time for the first time in the table, and it is the mean value of capability retention of the battery of no electrolyte leakage.
Table 11
| Battery | Charge-discharge cycles | Ability conservation rate (%) | The leakage cell ratio |
| B1 (scribbling Y) B2 (scribbling Sc) B3 (scribbling La) B4 (scribbling Ce) B5 (scribbling Pr) B6 (scribbling Nd) | 5 10 25 50 75 100 5 10 25 50 75 100 5 10 25 50 75 100 5 10 25 50 75 100 5 10 25 50 75 100 5 10 25 50 75 100 | 100 100 100 100 100 100 100 100 100 100 99 97 100 100 100 100 100 99 100 100 100 100 99 98 100 100 100 100 100 98 100 100 100 100 100 97 | 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 1/10 0/10 0/10 0/10 0/10 0/10 1/10 0/10 0/10 0/10 0/10 1/10 1/10 0/10 0/10 0/10 0/10 0/10 1/10 0/10 0/10 0/10 0/10 0/10 1/10 |
Table 12
| Battery | Charge-discharge cycles | Ability conservation rate (%) | The leakage cell ratio |
| B7 (scribbling Pm) B8 (scribbling Sm) B9 (scribbling Eu) B10 (scribbling Gd) B11 (scribbling Tb) B12 (scribbling Dy) | 5 10 25 50 75 100 5 10 25 50 75 100 5 10 25 50 75 100 5 10 25 50 75 100 5 10 25 50 75 100 5 10 25 50 75 100 | 100 100 100 100 98 96 100 100 100 100 99 99 100 100 100 99 98 98 100 100 100 100 100 98 100 100 100 99 97 93 100 100 100 96 94 91 | 0/10 0/10 0/10 0/10 1/10 2/10 0/10 0/10 0/10 0/10 0/10 1/10 0/10 0/10 0/10 0/10 1/10 2/10 0/10 0/10 0/10 0/10 0/10 1/10 0/10 0/10 0/10 0/10 1/10 2/10 0/10 0/10 0/10 1/10 2/10 3/10 |
Table 13
| Battery | Charge-discharge cycles | Ability conservation rate (%) | The leakage cell ratio |
| B13 (scribbling Ho) B14 (scribbling Er) B15 (scribbling Tm) B16 (scribbling Yb) B17 (scribbling Lu) | 5 10 25 50 75 100 5 10 25 50 75 100 5 10 25 50 75 100 5 10 25 50 75 100 5 10 25 50 75 100 | 100 100 100 99 97 94 100 100 100 100 100 100 100 100 100 99 97 93 100 100 100 100 100 100 100 100 100 99 95 92 | 0/10 0/10 0/10 0/10 1/10 3/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 1/10 3/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 2/10 3/10 |
, compare with comparison battery C1 to C3 shown in Figure 8 to 13 as can be seen from table 11, through long-term charging-discharge cycles, the capability retention of the 3rd battery B1 to B17 is higher, is difficult to leak.
(experiment 9)
In this experiment, the amount that is used to cover the Y that is coated with NiOOH and discharge capability and relation of leakage are studied.
Except the amount of Y is respectively 0.0343g, 0.1715g, 0.343g, 1.715g, 6.86g, 10.29g, 17.15g beyond 20.58g and the 24.01g, makes enclosed alkali storage battery b1, b2, b3, b4, b5, b6, b7, the method for b8 and b9 is identical with the 3rd battery B1.The condition of the charging-discharge cycle test of each battery is identical with experiment 1, thereby has obtained discharge capability and the discharge capability of 100 circulation times and the number of the battery that generation is leaked of circulation time for the first time.The results are shown in the table 14.In table 14, show discharge capability and the discharge capability of 100 circulation times and the number of battery that generation leak of the 3rd battery B1 at the circulation time first time.The discharge capability of the 1st time shown in the table 14 and 100 circulation times be the supposition second battery the first time circulation time discharge capability be the index that was drawn in 100 o'clock.The coated weight of the Y of NiOOH is respectively 0.01,0.05,0.1,0.5 in the ratio of Y and NiOOH among the battery b1 to b9,2,3,5,6,7 weight %.
Table 14
| Battery | Y content (weight %) | The discharge capability of the 1st circulation time | The discharge capability of the 100th circulation time | The leakage cell ratio |
| b1 b2 b3 b4 B1 b5 b6 b7 b8 b9 | 0.01 0.05 0.1 0.5 1 2 3 5 6 7 | 101 101 101 100 100 99 98 96 85 80 | 88 93 95 100 100 99 98 96 85 80 | 5/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 |
As can be seen from Table 14, the amount that applies the Y of NiOOH should be 0.05 to 5 weight %, so that the battery that acquisition has higher discharge capability and is difficult to leak.Confirmed that also if use other rare earth element or rare earth compound, the ratio calculation that the quantity of coating NiOOH is pressed rare earth element and NiOOH should be 0.05 to 5 weight %.Because the amount of Y is too little, makes the oxygen superpressure fully not increase, the discharge capability of the 100th circulation time battery b1 is too little, makes γ-NiOOH become β-NiOOH, thereby reduces to react the number of electronics.
(experiment 10)
In this experiment, valence mumber and the relation between discharge capability and the leakage of the Ni of NiOOH are studied.
Except the quantity of the clorox of 10 weight % in the sodium hydroxide solution of sneaking into 500ml becomes 100ml respectively, 200ml, outside 300ml and the 1000ml, enclosed alkali storage battery b10, b11, the manufacture method of b12 and b13 is identical with the 3rd battery B1.The charging of each battery-discharge cycle test condition is identical with experiment 1, thereby has drawn the discharge capability of circulation for the first time and the number of the battery that the 100th circulation time generation leaked.The results are shown in the table 15.In table 15, also show the number of battery cells that the 3rd battery B1 leaks in the discharge capability and the 100th the circulation time generation of the 1st circulation time.Each discharge capability in the table 15 is that supposition the 3rd battery B1 is the index that was drawn in 100 o'clock at the discharge capability of the 1st circulation time.
Table 15
| Battery | The valence mumber of Ni | The battery ability | The leakage cell ratio |
| b10 b11 b12 B1 b13 | 2.6 2.8 3.0 3.5 3.8 | 30 70 98 100 110 | 0/10 0/10 0/10 0/10 0/10 |
As can be seen from Table 15, the valence mumber that preferably adopts Ni be 3.0 to 3.8 NiOOH as active positive electrode material, thereby obtain to have the 3rd battery of big discharge capability.Confirm that also for second battery, the valence mumber that preferably also adopts Ni is that 3.0 to 3.8 NiOOH is as active positive electrode material.
(experiment 11)
In this experiment, at adopting NiOOH to have the 4th battery AB of the peak half width in 1.0 ° the crystal face (003) of X-ray diffraction pattern as active positive electrode material and NiOOH, and adopt the conventional batteries XB and the mixture that adopt nickel oxide and manganese dioxide conventional batteries XB as active positive electrode material of manganese dioxide as active positive electrode material, drawn the utilance of the 1st time and the 20th time circulation time active material by charging-discharge cycles.
(the 4th battery AB)
With 1 liter concentration is that the nickel sulfate solution of 1 mol and sodium hydroxide solution inject simultaneously and be contained in 25 ℃ thermostat and stir, and is 12.4 mixed aqueous solution thereby obtain the pH value.This solution was stirred one hour, leach the sediment that is produced, water cleans and is dry in vacuum in room temperature (about 25 ℃), thereby obtains Ni (OH)
2Then, 1 liter of mixed solution is heated to 60 ℃, adds the Ni that makes as mentioned above (OH) of 100g to it
2And stir, the concentration that comprises 500ml in this mixed liquor is that the sodium hydroxide solution of 10 mol and the concentration of 500ml are the aqueous sodium hypochlorite solution of 10 weight %.Resulting solution was stirred 1 hour, sediment is separated out, water cleans, and dry under 60 ℃, thereby obtains NiOOH.Utilize X-ray diffraction that NiOOH is analyzed with CuK α as radiation source under the described below condition, thereby draw near peak value half-breadth in the crystal face in the X-ray diffraction pattern (003) (peak value 2 θ=12 °).Half-breadth is 1.0 °.
[condition of X-ray diffraction analysis]
Counter electrode (Counter electrode): Cu
Tube voltage: 40kV
Tube current: 100mA
Filter: Ni
Scan rate: 2 °/min
Disperse seam: 1 °
Fig. 3 shows the part of X-ray diffraction pattern.In Fig. 3, h is illustrated in the peak height in the crystal face (003), and the peak width that h/2 highly locates is corresponding to half-breadth.Here half-breadth is represented with 2 θ, and it is corresponding to the length along 2 θ axle (transverse axis) half-breadths, by degree (°) measure, θ represents the Bragg angle.
Then, the NiOOH (active positive electrode material) that utilizes blender that 90g is obtained like this, the potassium hydroxide aqueous solution of 10g graphite and 10g 30 weight % mixed 30 minutes, with resulting material extrusion molding is the hollow cylindrical positive electrode, its external diameter is 1.3cm, internal diameter is 0.85cm, highly is 1.15cm.When making battery, three hollow cylindrical positive electrodes are concatenated into a hollow cylindrical positive electrode.
With the zinc powder of 65g, the potassium hydroxide aqueous solution of the 40 weight % of the ZnO that comprises 6 weight % (saturation value) of 34g and 1g acrylic resin (are made product code: polyacrylic acid 150) mix and make the colloid negative electrode by Nihon Junyaku company.
Except adopting top positive electrode and negative electrode, the manufacture method of the sealing Ni-Zn storage battery AB (the 4th battery) of AA size with first the experiment in embodiment 1 identical.
(relatively battery XB)
With the 100g manganese dioxide powder, 15g powdered graphite and 5g polyvinyl resin mix, and the concentration with 20ml is the potassium hydroxide aqueous solution mixing of 7 mol again.With formed material extrusion molding is the hollow cylindrical positive electrode.Except adopting this positive electrode, relatively the manufacture of battery XB is identical with the 4th battery AB.
(relatively battery YB)
With concentration be the liquor natrii hypochloritis 1500ml of the nickel nitrate 500ml of 2 mol and 10 weight % to be instilled into 2 liters concentration be in the potassium hydroxide solution of 14 mol, more formed mixture was slowly cooled off 1 hour.Then, leaching formed sediment, is the potassium hydroxide solution cleaning of 2 mol with concentration, and water cleans, and dry under 90 ℃ temperature, thereby obtains the nickel oxide powder as active positive electrode material.With the 50g nickel oxide powder, the 30g manganese dioxide powder, 15g powdered graphite and 5g polyvinyl resin mix, and the concentration with 20ml is the potassium hydroxide aqueous solution mixing of 7 mol again.With formed material extrusion molding is the hollow cylindrical active positive electrode material.Except adopting this positive electrode, relatively the manufacture method of battery YB is identical with the 4th battery AB.
[utilance of the active material of the 1st time and 20 each batteries of circulation time]
Each battery is charged-discharge cycle test, in each circulation, under the load of 3.9 Ω, make it to be discharged to 0.9V, charge to 1.95V, thereby obtain the 1st time and the utilance of 20 circulation time active materials by following formula at 150mA.Every type battery is utilized 10 batteries.The utilance of each battery that table 16 is listed is the mean value of the utilance of 10 batteries.
Active material utilization (%)={ discharge capability (mAh)/[amount of NiOOH (g) * 288 (mAh/g)] * 100
Table 16
| Battery | Active material utilization (%) | |
| The 1st circulation | The 20th circulation | |
| |
100 70 80 | 100 60 75 |
Shown in table 16, at the 1st time and 20 circulation times, the utilance of the active material of the 4th battery all is higher than conventional batteries XB and YB.This means NiOOH by adopting low-crystallinity as active positive electrode material, the utilance of the active material of resulting enclosed alkali battery is higher than conventional batteries.
(experiment 12)
In this experiment, obtained at the 1st time, have the utilance of the NiOOH of different half-breadths with the employing of eight types of 50 circulation times 20 times, thereby the relation between the utilance of the half-breadth of NiOOH and active material is studied as the active material of the enclosed alkali battery of active positive electrode material.
Except use makes Ni (OH)
2The pH value of the mixed solution of precipitation becomes 13.4 respectively, 13.2,13.0,12.7, outside 11.7 and 10.9, have 0.5 °, 0.6 °, 0.7 °, 0.8 °, 1.2 ° of manufacture methods with six types NiOOH of the peak value half-breadth of the crystal face (003) of 1.4 ° X-ray diffraction pattern are identical with the manufacture of the active positive electrode material of the 4th electrode A B.Then, according to making six types enclosed alkali Ni-Zn storage battery b with the identical mode of the 4th battery AB, c, d, e, f and g, different is as active positive electrode material with above-mentioned NiOOH.Charging-the discharge cycle test of every kind of battery with experiment 1 identical condition under carry out, thereby draw at the 1st time the utilances of 20 times and 50 times circulation time active materials.The results are shown in table 17.Also show the 4th battery AB in the table 17 at the 1st time, the utilance of 20 times and 50 times circulation time active materials.
Table 17
| Battery | Half- |
The 1st circulation | The 20th circulation of active material utilization (%) | The 50th circulation |
| b c d e AB f g | 0.5° 0.6° 0.7° 0.8° 1.0° 1.2° 1.4° | 90 94 100 100 100 100 100 | 84 89 95 100 100 100 100 | 61 70 86 100 100 100 100 |
Shown in table 17, the half-breadth that adopts low-crystallinity at the battery AB of the NiOOH more than 0.8 ° and e in g, not only the utilance of active material is all very high in the initial charge/discharge circulation but also in the 50th circulation.By contrast, the half-breadth that adopts better degree of crystallinity less than the battery b of 0.8 ° NiOOH in d, active material is lower in the utilance of the 50th circulation time.These results show, in order to obtain to have the battery of higher utilance in long-term charge and discharge cycles, must adopt half-breadth at the NiOOH more than 0.8 °.
(experiment 13)
In this experiment, comprise the solid solution element Bi at use, Cd, Co, Mn, Mg, the NiOOH of Y and Zn have drawn the 1st time as the enclosed alkali storage battery of active positive electrode material, the utilance of the active material of the 20th time and 50 circulation times.
Comprise Bi respectively, Cd, Co, Mn, Mg, Y is identical with the 4th battery AB as the preparation method of seven types NiOOH of solid solution element with Zn, and different is preparation Ni (OH)
2The time employed concentration be that 1 liter of nickel sulfate solution of 1 mol replaces to 1 liter of the nickel sulfate solution that concentration is 0.8 mol respectively, or be the bismuth sulfate solution of 0.2 mol by metal element substitution conversion concentration, cadmium sulfate solution, cobalt sulfate solution, manganese sulfate solution, 1 liter of Adlerika or sulfuric acid iridium solution.The ratio of the solid solution element of NiOOH recited above is 20%.Except adopting above-mentioned NiOOH as the active positive electrode material, make i, j, k, l, m, the method for this enclosed alkali storage battery of seven types of n and o is identical with the 4th battery AB.The charging of every kind of battery-discharge cycle test condition is identical with experiment 1, thereby obtains the 1st time, the ratio of the battery that the utilance of 20 times and 50 times circulation time active materials and generation are leaked.The results are shown in table 18
Table 18
| Battery | Half- |
The 1st circulation | The 20th circulation of active material utilization (%) | The 50th circulation |
| i j k l m n o | 1.0° 1.0° 1.0° 1.0° 1.0° 1.0° 1.0° | 100 100 100 100 100 100 100 | 100 100 100 100 100 100 100 | 100 100 100 100 100 100 100 |
It can also be seen that from table 18, use to comprise solid solution element Bi, Cd, Co, Mn, Mg is among the NiOOH of Y and Zn, because employed NiOOH degree of crystallinity is low, half-breadth is more than 0.8 °, charge for a long time-utilance of discharge cycles active material keeps higher, can not leak.
Because long-term charging-discharge cycles electrolyte is difficult to leak, as a kind of height reliable battery, enclosed alkali storage battery of the present invention is practical.
Claims (12)
1. an enclosed alkali storage battery comprises: active positive electrode material NiOOH; With the negative electrode that constitutes by negative electrode active material, it is zinc, cadmium or hydrogenation hydrogen-absorbing alloy electrode, this active positive electrode material and this negative electrode active material all are contained in the battery case, account for more than 75% of battery case volume, have at least a rare earth element and/or at least a rare earth compound among the NiOOH as additive, wherein, the ratio of rare earth element and NiOOH is 0.05 to 5 weight %.
2. enclosed alkali storage battery as claimed in claim 1, wherein before the 1st charging, the valence mumber of Ni is 3.0 to 3.8 among the NiOOH.
3. enclosed alkali storage battery as claimed in claim 1, wherein said rare earth element is select from the rare earth element group of Y, Er and Yb composition at least a, and described rare earth compound is select from the rare earth compound group that Y compound, Er compound and Yb compound are formed at least a.
4. enclosed alkali storage battery as claimed in claim 1, wherein, NiOOH comprises that at least a element of selecting in the group element of being made up of Mn, Zn, Co, Bi and rare earth element is as the solid solution element.
5. enclosed alkali storage battery as claimed in claim 1, wherein, the NiOOH that comprises solid solution element M n is the oxidation product that comprises the nickel hydroxide of solid solution element M n.
6. enclosed alkali storage battery as claimed in claim 1, wherein, negative electricity very zinc electrode and negative electrode active material is the mixture of Zn and zinc oxide.
7. an enclosed alkali storage battery comprises: active positive electrode material NiOOH; With the negative electrode that constitutes by negative electrode active material, it is zinc electrode, cadmium electrode or hydrogenation hydrogen-absorbing alloy electrode, this active positive electrode material and this negative electrode active material all are contained in the battery case, account for more than 75% of battery case volume, NiOOH is included in and scribbles a kind of rare earth element and/or rare earth compound coating on the particle surface at least, wherein, the ratio of rare earth element and NiOOH is 0.05 to 5 weight %.
8. enclosed alkali storage battery as claimed in claim 7, wherein before the 1st charging, the valence mumber of Ni is 3.0 to 3.8 among the NiOOH.
9. enclosed alkali storage battery as claimed in claim 7, wherein said rare earth element is select from the rare earth element group of Y, Er and Yb composition at least a, and described rare earth compound is select from the rare earth compound group that Y compound, Er compound and Yb compound are formed at least a.
10. enclosed alkali storage battery as claimed in claim 7, wherein, NiOOH comprises that at least a element of selecting in the group element of being made up of Mn, Zn, Co, Bi and rare earth element is as the solid solution element.
11. an enclosed alkali storage battery comprises: active positive electrode material NiOOH; With the negative electrode that constitutes by negative electrode active material, it is zinc electrode, cadmium electrode or hydrogenation hydrogen-absorbing alloy electrode, this active positive electrode material and this negative electrode active material all are contained in the battery case, account for more than 75% of battery case volume, spike half-breadth in the crystal face (003) of the X-ray diffraction pattern of NiOOH is more than 0.8 °, represent that by 2 θ θ is the Bragg angle.
12. enclosed alkali storage battery as claimed in claim 11, wherein, NiOOH comprises that at least a element of selecting in the group element of being made up of Bi, Cd, Co, Mg, Mn, Y and Zn is as the solid solution element.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03312697A JP3239076B2 (en) | 1997-01-30 | 1997-01-30 | Sealed alkaline storage battery |
| JP33126/97 | 1997-01-30 | ||
| JP9247778A JPH1167199A (en) | 1997-08-27 | 1997-08-27 | Tightly sealed type alkaline storage battery |
| JP247778/97 | 1997-08-27 | ||
| JP278118/97 | 1997-09-24 | ||
| JP9278118A JPH1197010A (en) | 1997-09-24 | 1997-09-24 | Sealed alkaline storage battery |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB988021188A Division CN100361330C (en) | 1997-01-30 | 1998-01-12 | Enclosed alkali storage battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101188292A true CN101188292A (en) | 2008-05-28 |
| CN101188292B CN101188292B (en) | 2010-06-02 |
Family
ID=12377932
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007101698909A Expired - Fee Related CN101188292B (en) | 1997-01-30 | 1998-01-12 | Sealed alkaline storage battery |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP3239076B2 (en) |
| CN (1) | CN101188292B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110400941A (en) * | 2019-08-29 | 2019-11-01 | 福建南平南孚电池有限公司 | A kind of method improving alkaline Mn cell discharge performance by moisturizing and water replanishing device |
| CN113346082A (en) * | 2021-05-28 | 2021-09-03 | 浙江野马电池股份有限公司 | Alkaline manganese battery with sodium alginate and preparation method thereof |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6258482B1 (en) | 1998-05-19 | 2001-07-10 | Sanyo Electric Co., Ltd. | Hydrogen storage alloy electrode and method for fabrication thereof |
| CA2274285C (en) | 1998-06-12 | 2003-09-16 | Mitsunori Tokuda | Sealed, alkaline-zinc storage battery |
| JP2000277104A (en) * | 1999-03-25 | 2000-10-06 | Sanyo Electric Co Ltd | Sealed type alkaline storage battery |
| JP2001060455A (en) * | 1999-06-17 | 2001-03-06 | Sanyo Electric Co Ltd | Sealed alkaline storage battery |
| JP3728143B2 (en) * | 1999-06-22 | 2005-12-21 | 三洋電機株式会社 | Sealed alkaline storage battery |
| JP2001035489A (en) * | 1999-07-22 | 2001-02-09 | Sanyo Electric Co Ltd | Sealed alkaline storage battery |
| TW520575B (en) * | 2000-04-21 | 2003-02-11 | Sony Corp | Positive electrode material and nickel-zinc battery |
| JP4846115B2 (en) * | 2000-10-04 | 2011-12-28 | 株式会社田中化学研究所 | Method for producing nickel oxyhydroxide |
| JP4765195B2 (en) * | 2001-05-10 | 2011-09-07 | ソニー株式会社 | Positive electrode active material, method for producing positive electrode active material, positive electrode for battery, and battery |
| JP2004154419A (en) | 2002-11-07 | 2004-06-03 | Sony Corp | Signal processing apparatus and method, recording medium and program |
| JPWO2005045958A1 (en) * | 2003-11-06 | 2007-11-29 | 松下電器産業株式会社 | Method for producing alkaline battery and positive electrode material for alkaline battery |
| CN100383997C (en) * | 2003-11-06 | 2008-04-23 | 松下电器产业株式会社 | Alkaline battery and positive electrode material for alkaline battery |
| CN1947285A (en) | 2004-04-23 | 2007-04-11 | 松下电器产业株式会社 | Alkaline battery and method for producing positive electrode material therefor |
| EP1811593A4 (en) * | 2004-10-15 | 2010-12-08 | Panasonic Corp | Alkaline battery |
| WO2020218594A1 (en) * | 2019-04-26 | 2020-10-29 | 京セラ株式会社 | Secondary battery and secondary battery system |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3097347B2 (en) * | 1992-09-18 | 2000-10-10 | 松下電器産業株式会社 | Nickel-metal hydride battery |
-
1997
- 1997-01-30 JP JP03312697A patent/JP3239076B2/en not_active Expired - Lifetime
-
1998
- 1998-01-12 CN CN2007101698909A patent/CN101188292B/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110400941A (en) * | 2019-08-29 | 2019-11-01 | 福建南平南孚电池有限公司 | A kind of method improving alkaline Mn cell discharge performance by moisturizing and water replanishing device |
| CN110400941B (en) * | 2019-08-29 | 2024-03-01 | 福建南平南孚电池有限公司 | Method for improving discharge performance of alkaline manganese cell through water supplementing and water supplementing device |
| CN113346082A (en) * | 2021-05-28 | 2021-09-03 | 浙江野马电池股份有限公司 | Alkaline manganese battery with sodium alginate and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3239076B2 (en) | 2001-12-17 |
| CN101188292B (en) | 2010-06-02 |
| JPH10214621A (en) | 1998-08-11 |
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