CN1265486C - En closed nickel-zinc primary battery, its anode and prodn methods for them - Google Patents

Abstract

A high-capacity enclosed nickel-zinc primary battery excellent in characteristics such as capacity maintenance factor, energy density, and high-efficient discharge characteristics, an anode using it, and a production method for them. An enclosed nickel-zinc primary battery which uses as an anode an anode active material of nickel hydroxide compound, such as nickel oxyhydroxide, particles and uses zinc alloy gel as a cathode material, wherein a ratio of anode theoretical capacity to cathode theoretical capacity is 1.0-1.6, and a ratio of alkali electrolyte to anode theoretical capacity is 1.0-1.6 ml/Ah.

Description

En closed nickel-zinc primary battery, its positive pole and their manufacture method

Technical field

The present invention relates to a kind of en closed nickel-zinc primary battery, its positive pole and their manufacture method.

Background technology

Power supply as for example portable electronic devices such as portable receiver or cassette recorder uses airtight shape alkaline primary battery etc.

The positive active material of using as alkaline battery generally uses manganese dioxide.

The latest development of various portable electronic devices makes one notice, and increasing device needs the heavy load characteristic.Therefore, require a kind of more excellent battery of alkaline manganese battery that aspect the high efficiency flash-over characteristic, more generally uses.

Existing battery comprises the battery that has by coiling sheet positive pole, negative pole and dividing plate and inject the helical structure that electrolyte makes, and cylindrical shape positive pole, gelled negative electrode and cylindrical shape dividing plate are received and kept the battery of counter-rotating (inside-out) structure in the cylindrical metal jar.

The counter-rotative type battery than the battery excellence of spiral-shaped structure, and can provide higher capacity under low price aspect productivity ratio.Yet because the opposed area of anodal and negative pole is little, the counter-rotative type battery is relatively poor aspect the high efficiency flash-over characteristic.

On the other hand, the battery of also known another kind excellence aspect the high efficiency flash-over characteristic, its for use nickel oxide as anodal, zinc as negative pole, alkaline salt solution nickel-zinc cell (No. 365125, British patent) as electrolyte.

In addition, this battery also has many advantages, comprises (1) cell voltage height, and (2) discharge curve is smooth, and (3) utilance height under high rate discharge.

Yet this battery is practicability not as yet.

Its reason is to produce the problem in the short useful life that dendritic crystal and alteration of form caused by zincode in the charging and discharging circulation and do not solve fully as yet.

The also known another kind of nickel hydroxide that uses is as positive active material, the zinc counter-rotative type Ni-MH secondary battery (the Japan Patent spy opens 2000-67910 number) as negative electrode active material.

Yet this battery relates to owing to the recharge discharge cycles, and oxygen produces from anodal during charging, presses liter in the battery, the problem that electrolyte can be sewed.

In addition, the positive pole of this battery is 1: 2 with the theoretical capacity ratio of negative pole.This is the means to save the situation of deterioration as preventing that gas from producing that prevents battery behavior, but stays the negative electrode active materials that are not used to discharge in a large number owing to causing, and is difficult to realize high power capacity.

About nickel-zinc primary battery, its development does not up to now almost have report.

Therefore, first purpose of the present invention is for providing a kind of above-mentioned excellent specific property that keeps existing nickel-zinc cell, having high power capacity and the en closed nickel-zinc primary battery of capacity sustainment rate excellence when storing.

Second purpose of the present invention is for providing a kind of counter-rotative type nickel-zinc primary battery of high efficiency flash-over characteristic excellence.

The energy density high en closed nickel-zinc primary battery of the 3rd purpose of the present invention for a kind of per unit mass is provided.

The 4th purpose of the present invention is for providing a kind of method of making above-mentioned en closed nickel-zinc primary battery.

The 5th purpose of the present invention is for providing a kind of positive pole and manufacture method thereof that is used for above-mentioned en closed nickel-zinc primary battery.

Summary of the invention

The invention provides the en closed nickel-zinc primary battery of various ways, anodal and these batteries that are used for them and the manufacture method of positive pole.

By using specific nickel hydroxide, be suitable for the structure of primary cell according to en closed nickel-zinc primary battery of the present invention, can guarantee above-mentioned excellent specific property with formation as its positive active material.

This feature can be passed through the optimization of (1) negative pole/anodal theoretical capacity ratio, and (2) are with respect to the electrolyte ratio optimization of anodal theoretical capacity, and the optimum range of (3) decision alkaline electrolyte conductance obtains.

In order to realize that according to en closed nickel-zinc primary battery of the present invention the fillibility, the raising discharge vessel that improve positive active material are very important.Therefore, these characteristics can form spherical positive active material and remarkable improvement by (4).

In order to improve the self-discharge of battery, can on the surface of positive active material, form high order cobalt/cobalt oxide layer by (5), (6) are used NaOH and LiOH to add alkaline electrolyte as additive and are further improved.

In addition, battery according to the present invention can be implemented in the battery of the property produced in batches aspect excellence by having inversion structures.

Promptly, according to a first aspect of the invention, a kind of en closed nickel-zinc primary battery that uses the nickel series compounds particle as its main positive active material is provided, it is characterized in that, the ratio of anodal theoretical capacity anticathode theoretical capacity is 1.0～1.6, and alkaline electrolyte is 1.0～1.6ml/Ah to the ratio of anodal theoretical capacity.

In the present invention, term " uses the nickel series compounds particle as positive active material " and represents that the whole or most of of component of battery positive electrode active material are made of the nickel series compounds particle, as MnO ₂And so on known positive active material can be blended in this positive active material that constitutes by the nickel series compounds particle.

In a first aspect of the present invention, preferably, battery is by containing anodal formed body that above-mentioned nickel series compounds particle forms as the anode mixture compression molding of positive active material, receiving and keeping in metal can and constitute being dispersed in the negative electrode gel that forms in the alkaline electrolyte and dividing plate with zinc as the alloy powder of key component, the non-solid part of above-mentioned anodal formed body is preferably 0.2: 1 with the volume ratio of positive active material～and 0.5: 1, but not the volume occupation rate that solid portion accounts in above-mentioned anodal formed body is preferably 15～30 volume %.

If en closed nickel-zinc primary battery has inversion structures, can realize having the en closed nickel-zinc primary battery of good capacity efficient.

Positive active material is preferably oxynickel hydroxide (nickel oxyhydroxide) particle, and the oxynickel hydroxide particle more preferably contains γ-oxynickel hydroxide.

As positive active material, oxynickel hydroxide particle and eutectic zinc and cobalt one or the oxynickel hydroxide particle of the two be suitable material, and above-mentioned positive active material also can contain the compound that is selected from least a metal in yttrium, ytterbium, erbium and the calcium.

Positive active material has been preferably oxynickel hydroxide particle that the surface covers with cobalt high suboxide, metallic cobalt or metallic nickel or eutectic zinc and the one of cobalt or the oxynickel hydroxide particle of the two.The high suboxide of cobalt that covers positive active material is at least a material that is selected from oxygen cobalt hydroxide, cobaltosic oxide, cobalt sesquioxide, cobalt black and cobalt hydroxide.

Positive active material is preferably the oxynickel hydroxide particle that is covered by the high suboxide of cobalt to be formed, and in differential thermal analysis, this particle preferably shows endothermic peak in 200～260 ℃.The nickel series compounds particle that forms the positive active material that covers has the resistivity that is not higher than 100 Ω cm.Positive active material of the present invention is preferably by the oxynickel hydroxide based compound particle spherical, that standard is spherical or the two aggregate is formed.

Preferably be added with carbon granule in the above-mentioned anode mixture that contains positive active material of the present invention, the amount that carbon granule accounts for anode mixture is 3～15 quality %, more preferably its 3～10 quality %.

Can select specific area is 1.0～300m ²The carbon granule of/g.

Above-mentioned carbon granule is preferably the carbon granule group's of at least two kinds of different specific areas mixture.Above-mentioned carbon granule more preferably, 25～75 quality % specific areas are 1.0～30m ²/ g carbon granule and 75～25 quality % specific areas are 30～300m ²The mixture of/g carbon granule.

To contain stearic acid compound as the anode mixture of its key component as the nickel series compounds particle of positive active material and carbon granule.Stearic acid compound preferably is mixed in the anode mixture with ratio 0.05～0.5 quality %.

Be used for alkaline electrolyte according to en closed nickel-zinc primary battery of the present invention, preferably by be selected from potassium hydroxide, NaOH and lithium hydroxide at least one as its solute, its conductance is preferably and is not less than 0.2S/cm.

In a first aspect of the present invention, the counter-rotative type battery can be by receiving and keeping in a battery case: the anodal formed body of hollow circle tube of the compression molding preparation by the anode mixture mixture, this anode mixture with the nickel series compounds particle formed by spherical, accurate spherical or the two aggregate as positive active material; Be disposed at the dividing plate of the hollow bulb of the anodal formed body of hollow circle tube; And comprise alkaline electrolyte and insert the negative electrode gel in the dividing plate and form.

According to a second aspect of the invention, a kind of method of making en closed nickel-zinc primary battery is provided, it is characterized in that: with spherical, accurate spherical or the two the nickel series compounds particle of aggregate as positive active material, at least mix carbon granule in above-mentioned positive active material and the preparation anode mixture, it is granular that granulation becomes; By compression molding it is configured as the anodal formed body of a hollow circle tube; The anodal formed body of above-mentioned hollow circle tube is received and kept in metal can; Dividing plate is inserted the hollow cylinder inside of above-mentioned anodal formed body; Be stored in that to be dispersed with in the alkaline electrolyte with zinc be the negative electrode gel that the alloy powder of main component forms; Negative electrode collector is inserted in the gelled negative electrode; With one jar of opening that coffer is airtight above-mentioned jar.

The manufacture method of this en closed nickel-zinc primary battery preferably includes that above-mentioned to be positive active material and carbon granule with nickel series compounds become granular step as the mixture granulation of the anode mixture of its key component, and stearic acid compound is added step in this granular anode mixture.

In the manufacture method of en closed nickel-zinc primary battery, implement high-temperature aging after being preferably in assemble.It is to implement 24～72 hours under 40～80 ℃ that high-temperature aging is preferably in temperature range.

In the manufacture method of en closed nickel-zinc primary battery, preferably nickel series compounds being stored under the temperature that is not higher than 30 ℃ before the battery assembling carried out.

According to a third aspect of the invention we, provide a kind of by the battery that the anode mixture mixture compression molding as positive active material with the nickel series compounds particle is prepared compression nickel series compounds positive pole, above-mentioned nickel series compounds particle is spherical, accurate spherical or the aggregate of the two.The average grain diameter of nickel series compounds particle is preferably 1～50 μ m.

According to a forth aspect of the invention, provide a kind of method of making battery with compression nickel series compounds positive pole, comprising: mix and the stirring inorganic nickel aqueous solution and alkaline aqueous solution, separate out the step of nickel hydroxide based compound particle; Cover the step of above-mentioned nickel hydroxide based compound particle surface with cobalt compound; Oxidation converts it into the step of the oxynickel hydroxide based compound particle that is covered by cobalt compound by the above-mentioned nickel hydroxide based compound particle that above-mentioned cobalt compound covers; The anode mixture additive is added in the oxynickel hydroxide based compound particle that is covered by above-mentioned cobalt compound, and the step of the anode mixture mixture of granulation generation; And be the step of anodal formed body with the compression molding of above-mentioned granulation anode mixture.

In the more preferably manufacture method of battery with compression nickel series compounds positive pole, the anode mixture additive is added in the above-mentioned oxynickel hydroxide based compound particle by the cobalt compound covering, and the step of the anode mixture mixture of granulation generation, comprise at least: the mixture of above-mentioned anode mixture is imported the procedure of processing that rolls for preparing compressing powder between two rollers; Above-mentioned compressing powder is imported the granulation procedure of processing of between the two rollers that have chimeric protuberance on its roller surface, carrying out granulation; And use sieve that this granulated powder is classified into the classification procedure of processing of particle size range arbitrarily.

In the method, prepare the rolling in the procedure of processing of compressing powder between above-mentioned pair of roller above-mentioned above-mentioned anode mixture mixture is imported, two roller per unit lengths apply 1.5 * 10 ⁴～3.5 * 10 ⁴The stress of N/cm is to the mixture of above-mentioned anode mixture.Above-mentioned use sieve becomes above-mentioned efflorescence powder classification that grading range is 200～800 μ m in the classification procedure of processing of particle size range arbitrarily.Above-mentioned will be through the anode mixture compression molding of granulation grain, classification and prepare in the step of anodal formed body, anodal shaping density is 2.7～3.5g/cm ³

Description of drawings

Fig. 1 is for using the sectional view of counter-rotative type battery of the present invention;

Fig. 2 is the flow chart of displaying according to the step of a variation of the manufacture method of the en closed nickel-zinc primary battery of second aspect present invention;

Fig. 3 is for showing the chart of effect of the present invention;

Fig. 4 is for showing the chart of effect of the present invention;

Fig. 5 is for making the skeleton diagram of the spherical nickel hydroxide particle device that is suitable for positive active material of the present invention.

Embodiment

[structure of en closed nickel-zinc primary battery]

Below, present invention will be described in detail with reference to the accompanying.

Fig. 1 shows the example that is applied to LR6 type (single 3 shapes, or the make size AA) battery according to the JIS standard of the present invention, and it has so-called inversion structures (tank body of battery is as the lid of anodal, the battery structure as positive pole).

In Fig. 1, Reference numeral 1 expression has the metal can of the airtight drum forms in bottom, and it is also as anodal.In the inside of metal can 1, form anode mixture 2 hollow cylindrical body, that contain mainly the positive active material that the spherical particle by nickel series compounds constitutes, received and kept in the mode that contacts with metal can 1 inner surface.

Gel zinc negative material 4 clips the dividing plate of being made by for example nonwoven fabrics that the round-ended cylinder shape is arranged 3, is packed in the cavity of anode mixture 2.

Insert the negative electrode collector rod 5 that metal bar constitutes in negative material 4, an end of this negative electrode collector rod 5 is outstanding from negative material 4 surfaces, is electrically connected with the metal hush panel 8 of double as negative terminal with annular metal sheet 7.

The insulating washer 6 that is made of plastic resin such as polyamide etc. of dicyclo form is configured on the expose portion outer surface as the inner surface of anodal metal can 1 and negative electrode collector rod 5 their mutual insulatings.

The openend of metal can 1 is by calking and fluid-tight.

[method for designing of en closed nickel-zinc primary battery]

Below explanation realizes the required battery design method of above-mentioned en closed nickel-zinc primary battery.

(1) the negative pole theoretical capacity is to the determination of ratio of anodal theoretical capacity

By setting the Capacity Ratio (being designated hereinafter simply as Capacity Ratio) that various negative pole theoretical capacities obtain divided by anodal theoretical capacity, can design the battery of positive pole with pondage.

In order to design nickel-zinc cell as secondary cell, needing Capacity Ratio is 2～3.Therefore, in order to be stored in the predetermined tank body, can calculate battery capacity from anodal and negative pole theoretical capacity is 1500mAh～1900mAh.

On the other hand, low because Capacity Ratio can be set in the present invention who is designed to primary cell to 1.0～1.6, so compare, can realize the most about 70% high capacity with the design of secondary cell.

In this proposed, Capacity Ratio was that peaked main reason is that the discharge band of anodal oxynickel hydroxide is not to be 1.0 valencys forever with 1.6, can use the discharge band of about 1.5 valencys from the γ oxynickel hydroxide to the α nickel hydroxide under certain condition.

That is, the design of primary cell needs not exceed 1.6 Capacity Ratio.

(2) with respect to the electrolyte ratio of anodal theoretical capacity and the relation between the anodal utilance

Usually, battery design uses one of anodal and negative pole to implement as the capacity regulating utmost point.

Once or secondary alkaline batteries use its positive pole to design usually as the capacity regulating utmost point, to set anodal theoretical capacity a little less than the negative pole theoretical capacity.

Therefore, the optimum amount of electrolyte can use it with respect to the ratio of anodal theoretical capacity and determine.

For this purpose, fixing anodal theoretical capacity, the ratio of change electrolyte, the decision experiment optimal proportion of electrolyte.

(3) electrolyte form and conductance between and the relation between anodal utilance and the capacity sustainment rate thereof

About the conductance of electrolyte because itself and anodal theoretical capacity concern no less important, go through so do one for the relation of the factor of these battery behaviors and anodal theoretical capacity.

By these programs, can design and make the best battery of realizing the object of the invention.

In en closed nickel-zinc primary battery of the present invention, the volume of the non-solid part of anode mixture in the composition of formation anode mixture, that be impregnated with electrolyte in it, it is very big to influence battery behavior, by in anode mixture, the volume occupation rate (non-solid part is to the volume ratio of anode mixture) of setting non-solid part in the volume ratio of non-solid part and positive active material and the anode mixture can get the battery of the special excellent high capacity of high efficiency flash-over characteristic in particular range.This battery below is described.

Promptly, when the volume of the non-solid part of anode mixture when defining shown in (1), the key property of battery is, the volume of the non-solid part of anode mixture and the volume ratio of positive active material are 0.2: 1～0.5: 1, and the volume occupation rate of the non-solid part in the anode mixture is 15～30 volume %.

(volume of non-solid part)=(volume of the anode mixture of filling)-{ (volume of positive active material)+(volume of the solid beyond the positive active material) } ... formula (1)

In formula (1), the volume of non-solid part comprises, for example, except the anode mixture internal pore, the electrolyte that when being shaped, adds, the water-soluble binder of gelation etc. with filling, in addition, as the volume of the solid except positive active material, comprise electric conducting material as carbon granule etc.

As mentioned above, the battery characteristics according to such scheme of the present invention is that in above-mentioned anode mixture, the volume of the non-solid part of anode mixture and the volume ratio of positive active material are 0.2: 1～0.5: 1.If the ratio of volume that is occupied by non-solid part and the volume that occupied by positive active material in anodal is less than this scope, with the moisture in the required electrolyte of the exoelectrical reaction as the oxynickel hydroxide of positive active material of following formula (2) expression, on the surface of positive active material particle, can locally lack, thereby stop the reaction of battery, therefore can reduce the high efficiency flash-over characteristic.

Formula (2)

On the other hand, if in anodal by the ratio of non-solid part volume that occupies and the volume that occupies by positive active material during greater than this scope, the contact point between solid particle can reduce, and can reduce the conductance of whole positive pole and reduce the high efficiency flash-over characteristic.

Therefore, anodal interior ratio by non-solid part volume that occupies and the volume that is occupied by positive active material is preferably 0.2: 1～0.5: 1, more preferably 0.25: 1～0.4: 1, is preferably 0.28: 1～0.34: 1 again.

In addition, battery characteristics according to the above embodiment of the present invention is that the volume occupation rate of non-solid part is 15～30 volume % in anode mixture.If not the volume occupation rate of solid portion less than this scope, makes the positive pole that is filled in the metal can take place damaged or be full of cracks easily, can damage the charge-trapping characteristic of whole positive pole and reduce discharge capacity.

If not the volume occupation rate of solid portion, is filled in the fabrication strength of the positive pole in the metal can greater than this scope and can weakens, can cause seriously coming off and reducing discharge capacity of in manufacturing process subsequently active material.

Therefore, in the present invention, the volume occupation rate of non-solid part is preferably 15～30 volume %, and more preferably 18～27 volume % are preferably 20～24 volume % again.

In addition, in the battery of this embodiment, conductance can be improved by mix carbon granule in anode mixture.Yet the content of the carbon granule in the anode mixture is preferably below the 10 quality %.

In the battery of this embodiment, if the content of carbon granule is too big in the anode mixture, the quality that can be contained in the positive active material itself in the conditional volume of metal can reduce, and can be quickened self-discharge and be reduced discharge capacity by the carbonic acid ion of the oxidation generation of carbon granule.

Therefore, the content of carbon granule is preferably below the 10 quality % in the anode mixture, more preferably below the 7 quality %.

For such design according to en closed nickel-zinc primary battery of the present invention, below, the manufacture method of positive electrode, negative material, electrolyte and battery is described in detail in detail according to this.

[positive electrode]

(positive active material)

The used positive active material of the present invention is mainly by nickel series compounds, and especially the particle of nickel hydroxide based compound such as nickel hydroxide, oxynickel hydroxide etc. constitutes.

In these materials, when the advantage of oxynickel hydroxide is high concentration, the cell voltage height, and discharge capacity also increases.

In addition, to contain zinc or cobalt separately or the two is the nickel hydroxide based compound of eutectic form, especially the eutectic oxynickel hydroxide is preferred, even because its structural change also seldom can be guaranteed stable discharging under low electrolyte ratio.

The zinc of eutectic or the amount of cobalt are preferably 1～12% in oxynickel hydroxide or other nickel hydroxide based compound, and more preferably 4～7%.

If the zinc amount is below 1%, utilance can reduce, and under certain conditions, anodal expansion can change the shape of battery.If it is higher than 12%, nickel purity can reduce relatively, and the minimizing of gained proportion can reduce capacity density, and high capacity can't be accepted.

The surface that comprises the nickel hydroxide based compound particle of these eutectic particles, preferably cover by at least a material that is selected from oxygen cobalt hydroxide, four oxidations, two cobalts, cobalt sesquioxide, cobalt oxide, cobalt hydroxide, metallic nickel and metallic cobalt, because have the surface-coated of the material of high conductivity, can increase the conductance of whole positive pole and can improve discharge capacity and high efficiency flash-over characteristic by this.

Tectal amount is 2.0～6.0 quality % with respect to positive active material preferably.

If tectal amount surpasses this scope, can produce expensive problem.If it is lower than this scope, then produce the problem of current collection performance deterioration.

From guaranteeing the viewpoint of the electron conduction between the oxynickel hydroxide particle, the compound positive hydroxide that uses deposition to have the cobalt high order compound of high conductivity is preferred.

About being deposited on this lip-deep cobalt compound,, can use cobalt hydroxide (Co (OH) as raw material ₂), cobalt black (CoO), cobalt sesquioxide (Co ₂O ₃) etc., its oxidation processes is transformed into high conduction high order cobalt oxide such as cobalt hydroxide (CoOOH), cobaltosic oxide (Co ₃O ₄) etc.

(manufacture method of positive active material)

Can be according to above-mentioned positive active material of the present invention by the method manufacturing for example.

In the nickel hydroxide particle that is doped with zinc and cobalt, add cobalt hydroxide, spray sodium hydrate aqueous solution while in atmosphere, stir.

Subsequently, by microwave heating, on the surface of nickel hydroxide particle, form a high order cobalt oxide layer, to obtain the compound nickel hydroxide particle of conductance excellence.

And, by with oxidant as follows sodium chloride etc. add the effect of above-mentioned reaction system accelerating oxidation, obtain to use up the compound oxynickel hydroxide particle that overall height time cobalt oxide layer covers, obtain the positive active material of conductance excellence thus.

In addition, also can cover the surface of nickel hydroxide particle with cobalt or cobalt compound particle, and get compound nickel hydroxide by in the particle of mainly making, mixing cobalt granule or cobalt compound particle, adhesive such as CMC and water by nickel hydroxide.

Cobalt granule or the cobalt compound particle that use this moment, preferably using specific area is 2.5～30m ³The cobalt hydroxide of/g.

When cobalt granule in this scope of use or cobalt compound particle, can guarantee the abundant contact area between nickel hydroxide and cobalt hydroxide, and this can cause the improvement of anodal utilance.

The manufacturing of such anode mixture is described in Japanese patent laid-open 10-233229 number, 10-275620 number and 10-188969 number, and the manufacture method of these anode mixtures also can be used for the present invention.

Preferably, the oxynickel hydroxide particle that covers high order cobalt oxide surface is presented at 200～260 ℃ scope in differential thermal analysis have endothermic peak, and more preferably, the resistivity of the particle that this is capped is 100 Ω cm or following.

Preferably, the oxynickel hydroxide particle preferably contains the γ oxynickel hydroxide.

Promptly, to the structure of the positive pole mainly made by the oxynickel hydroxide particle, and the result of electrode or battery behavior research, when confirmation endothermic peak in differential thermal analysis (DTA) dropped on 200～260 ℃ of scopes, the oxynickel hydroxide particle that is covered by the high order cobalt compound showed excellent especially discharge capacity.

That is, when endothermic peak surpasses 260 ℃ or below 200 ℃ the time, the smaller and high activity of discharge capacity slightly loses; Yet, when the endothermic peak scope is 200～260 ℃, can get the most excellent high efficiency flash-over characteristic.

Being covered and had the endothermic peak scope in differential thermal analysis by the high order cobalt compound is 200～260 ℃ oxynickel hydroxide particle, when its resistivity value is not higher than 1000 Ω cm, when preferably not being higher than 300 Ω cm, shows excellent high efficiency flash-over characteristic.

At this moment, possible cause is that when resistivity was higher than 100 Ω cm, the high order cobalt compound of covering surfaces contained material not too active on a large amount of electrochemistry such as Co ₃O ₄Deng.

And, usually, by the high order cobalt compound cover and in differential thermal analysis at 200～260 ℃ of oxynickel hydroxide particles with endothermic peak, be preferably β-oxynickel hydroxide and γ-oxynickel hydroxide and be.

γ-oxynickel hydroxide has than higher valency of β-oxynickel hydroxide and the oxygen overvoltage of Geng Gao.Yet its tendency causes the minimizing of apparent density, so the loading deficiency of active material can not obtain sufficient battery capacity.

β-oxynickel hydroxide has low oxygen overvoltage, and the problem of the capacity deterioration that self-discharge causes is arranged; Yet the problem of above-mentioned self-discharge is by improving with γ-oxynickel hydroxide coexistence.

In the positive active material of this embodiment, the oxynickel hydroxide particle can be single oxynickel hydroxide, but also can comprise in zinc and the cobalt at least one.

Oxynickel hydroxide particle by the covering of high order cobalt compound, can be by for example the nickel hydroxide particle that is covered by the high order cobalt compound being put into the aqueous solution of oxidant such as hydrogen peroxide or hypochlorite, dipping also stirs this solution, carries out the chemical oxidation effect and obtains.

Below the more specifically method according to the positive active material of this embodiment is made in explanation.

At first prepare with the powder (particle) of nickel hydroxide, with metallic cobalt, cobalt hydroxide, cobaltosic oxide (Co as its key component ₃O ₄) and cobalt oxide (CoO) in the mixed-powder of at least a powder.

The interpolation ratio of components of cobalt and cobalt compound is about 0.5～20 quality % usually, to guarantee required conductance and discharge capacity.

Secondly, mixed-powder is poured in the container that is suitable for stirring,, alkaline aqueous solution added obtain uniform mixture equipment in the mixing plant when mixed-powder during in container for stirring.

In the method, under the condition of oxygen coexistence, the system that heating (preferably be heated to temperature and be about 35～160 ℃) mixes.

In the process of heating, stirring and mixing, part cobalt or cobalt compound are dissolved in the alkaline aqueous solution with the compound ion form, become the high order cobalt oxide of the state that contains alkali, be dispersed in the particle with the form that covers the nickel hydroxide particle surface then, and form the precursor of conductive base.

Usually use sodium hydrate aqueous solution as alkaline aqueous solution herein; Yet, also can use the mixture of sodium hydrate aqueous solution and potassium hydroxide aqueous solution or lithium hydroxide aqueous solution.

The alkali concn preferable range is about 1～14N, with the dissolving and the compound ionization of steady promotion cobalt compound etc. or be beneficial to and form the conductive base of wanting.

Heater means is not limited to limited means, but sees that from the viewpoint of improving the utilance of active material microwave is very effective.

That is, mix hydrone in the mixing plant, heat the powdery components of nickel hydroxide particle etc. equably if microwave as thermal source, can shake, the result, conductive base can be formed uniformly on the surface of nickel hydroxide particle.

In addition, if microwave as thermal source, can confirm to produce in the crystalline texture of nickel hydroxide particle by the microwave energy of supply the state of defective or change micropore, the surface-active tendency of enhancing is arranged.

When microwave was used as thermal source, the time of microwave irradiation preferably was set at about 20 minutes.

Then, the aqueous sodium hypochlorite solution of 12 quality % of the sodium hydrate aqueous solution of 10 mol of the above-mentioned nickel hydroxide particle that is covered by the high order cobalt oxide of 100 mass parts, 500 mass parts, 500 mass parts is mixed, 800 ℃ of heating and stirring down.

After this heating and stirring,, make positive active material by the oxynickel hydroxide particle of high order cobalt covering surfaces washing of the sediment of gained and dried.

In en closed nickel-zinc primary battery of the present invention,, can improve the capacity sustainment rate when storing by in the positive active material of this nickel series compounds, adding Y, Er, Yb and Ca compound.

As the above-claimed cpd of using among the present invention, comprise for example Y ₂O ₃, Er ₂O ₃, Yb ₂O ₃Deng metal oxide and CaF ₂Deng metal fluoride.

These metal oxides and metal fluoride can be preferably 0.1～2 quality % with respect to being 0.1～10 quality % as the nickel hydroxide of positive active material etc., amount use.

The combined amount of this metal oxide or metal fluoride is when this scope is following, and storage characteristics can't improve.When combined amount surpasses this scope,, thereby be difficult to realize high capacity because the amount of positive active material can relatively reduce.

In the present invention, in the nickel series compounds that metal oxide or metal fluoride is joined nickel hydroxide etc., can realize by adding add the particle of these metal oxides or metal fluoride in the nickel hydroxide particle that in aqueous medium, disperses to.

The battery usefulness compression nickel series compounds positive pole that is applicable to according to en closed nickel-zinc primary battery battery of the present invention is described herein.

This positive pole is made with the mixture compression molding as the anode mixture of positive active material with the nickel series compounds particle by handle, and it is spherical, accurate spherical or the aggregate of the two that used nickel series compounds particle is characterised in that.

See that from the viewpoint that compression molding operation middle-high density is filled the average grain diameter of above-mentioned nickel series compounds particle is preferably 1～50 μ m.

Below, illustrate in greater detail according to this embodiment of the invention positive pole and manufacture method thereof.

(positive active material: spherical oxynickel hydroxide)

Material as being used for anodal nickel series compounds positive active material is preferably oxynickel hydroxide.

This oxynickel hydroxide particle can be by using following manufacture method to form spherical or being similar to spherical particle.

Spherical positive active material particle like this can increase packed density when compression molding, can realize high-capacity battery during as the counter-rotative type battery, so be preferred.

That is, by using the spherulite of oxynickel hydroxide, packed density can significantly be improved, and can about 2.7～3.5g/cm ³Satisfactory value.

The average grain diameter of used nickel series compounds particle is preferably 1～50 μ m, because it is the average grain diameter that high density is filled when being suitable for compression molding.

The oxynickel hydroxide based compound can comprise the zinc of eutectic form or cobalt is independent or the two.

This eutectic oxynickel hydroxide is because can reduce crystalline texture changes, so preferred.

Especially, by eutectic zinc, can improve the crystallography characteristic of oxynickel hydroxide, expand so can suppress the crystal in oxidation or when reduction, that is, the change of volume helps the battery design of low amount electrolyte.

And, under the situation of the nickel-zinc cell of making by the combination zincode and the oxynickel hydroxide utmost point, use a kind of means that prevent zincode self-discharge by saturated dissolved oxygen zinc in electrolyte.Yet the oxynickel hydroxide of non-eutectic absorbs the zinc ion that enters electrolyte when storing, and this effect can reduce.

In the case, can remove this adverse effect by the oxynickel hydroxide that uses prior doping zinc.

In addition, by with the cobalt eutectic, can improve the discharge utilance of oxynickel hydroxide.

When zinc and the equal eutectic of cobalt, can increase oxygen overvoltage, thereby can improve anodal self-discharge characteristic.

Eutectic in the oxynickel hydroxide zinc or the amount of cobalt be preferably 1～10%, more preferably 3～5%.

If zinc or cobalt amount are lower than this scope, decide on condition, battery can suffer the increase of self-discharge of minimizing, positive pole and the negative pole of anodal expansion, discharge utilance, so discharge capacity can reduce.

If amount surpasses this scope, nickel purity can relatively reduce, and is not suitable for high capacity.

From guaranteeing the viewpoint of the electron conduction between the oxynickel hydroxide particle, preferably, cover the compound positive hydroxide that the surface of nickel hydroxide obtains with the high order cobalt compound of high conductivity again.

(the manufacture method of positive active material: the manufacture method of spherical oxynickel hydroxide)

The oxynickel hydroxide particle passes through, 1) manufacturing of nickel hydroxide, the 2) manufacturing of the nickel hydroxide that covers with cobalt compound, and the 3) manufacturing of the oxynickel hydroxide that covers with cobalt compound, these operations are made.

This down will be according to each specification.

1) manufacturing of nickel hydroxide

Nickel hydroxide is made with the alkali neutralization then by metallic nickel is dissolved in the acid.

The used acid of this operation can be the inorganic acid of nitric acid or sulfuric acid etc., but from the viewpoint of the self-discharge that suppresses battery, preferably uses sulfuric acid.

In this operation, the dissolving of strong acid can be implemented by nickel powder being added stir simultaneously in sulfuric acid or the nitric acid.

In addition, in this operation, can implement by the nickel inorganic acid aqueous solution of previous steps gained is mixed with highly basic such as sodium hydrate aqueous solution etc. by the step of alkali neutralization.

In this operation, the crystallization of control nickel hydroxide is very important.

In the present invention, the spherulite of wanting can be by mixed Ni inorganic acid aqueous solution lentamente with inorganic base aqueous solution and firmly stir, and maintenance pH is about 11 and continuous stirring and obtaining.

As a result, can obtain the crystal that average grain diameter is about 10 μ m.

In this step, be about 11 in order to keep pH, except highly basic such as NaOH etc., preferably use ammonium salt simultaneously.

By the additional ammonium salt that uses, can obtain the particle that particle diameter is more even and have careful sphere.

The temperature of neutralization procedure is preferably 30～40 ℃.

If temperature is lower than this scope, be not suitable for supplying crystallographic component.

On the other hand, if temperature surpasses this scope, owing to use strong acid and strong alkali aqueous solution,, not preferred from the equipment cost of considering fail safe and operation etc.

Oxynickel hydroxide according to the present invention with eutectic under the form of zinc or the cobalt situation about using, when the metallic nickel dissolving entered strong acid, zinc, cobalt or its compound can dissolve simultaneously.

2) manufacturing of the nickel hydroxide that covers with cobalt compound

Then, cover the nickel hydroxide crystal of above-mentioned operation gained with cobalt hydroxide.

The covering of this cobalt hydroxide, for example utilize microwave etc. in containing the atmosphere of aerobic, by being that the cobalt compound of 1～5 μ m and spherical nickel hydroxide crystal that 100 mass parts average grain diameters are 10 μ m are in about 60～150 ℃ of heating to 5～7 mass parts average grain diameters, stir simultaneously, and spray the alkaline aqueous solution of NaOH etc. with the ratio of 5～20 mass parts, the cobalt hydroxide compound is dissolved in the alkaline aqueous solution, once more with Co (OH) ₂The form precipitation is separated out, and covers nickel hydroxide particle with film, is transformed into CoOOH or Co then ₃O ₄Deng high conduction cobalt high order compound.

As a result, can obtain having of high conductivity nickel hydroxide particle spherical and that cover by cobalt compound.

The manufacture method of the nickel series compounds that is covered by cobalt below is described in detail in detail.

At first, the nickel hydroxide particle of scheduled volume and cobalt hydroxide particle are dropped in the blender, stir and mixing.

When the inside of blender is the oxygen-containing atmosphere of atmosphere and so on, start heater means, stir, mix, the temperature of mixture is controlled to a predetermined temperature, heat-treat,, drive blender and mix simultaneously from the alkaline aqueous solution of nozzle supply predetermined concentration.

In this operation, along with the mixed uniformly of nickel hydroxide particle and cobalt compound particle carries out, Gong Ying alkaline aqueous solution sticks on the surface of mixture simultaneously, forms the reacting field of alkaline aqueous solution, cobalt compound particle and oxygen coexistence on the surface of nickel hydroxide particle.As a result, the cobalt compound particle becomes high suboxide, and covers the surface of nickel hydroxide particle.

As the cobalt compound particle, can distinguish and use metallic cobalt particle, cobalt hydroxide particle, three cobalt oxide particles, four cobalt oxide particles, cobalt black particle separately, also can use with the state of two kinds in them or multiple mixing.

In the case, the content of cobalt compound particle is preferably 0.5～20 quality % in the above-mentioned particle device.

If it is lower than 0.5 quality %, the formation meeting deficiency of conductive base on the surface of nickel hydroxide particle, utilance can not increase.If it is higher than 20 quality %, the regular meeting that compares of nickel hydroxide particle reduces, and can reduce discharge capacity.

As the alkaline aqueous solution that uses, can be that sodium hydrate aqueous solution, potassium hydroxide aqueous solution are independent, or their mixed liquor, or in above-mentioned solution is, mix the mixture that lithium hydroxide aqueous solution obtains.At this moment, the concentration of alkaline aqueous solution is preferably 1～14N.

When concentration is lower than 1N, the solubility that is contained in the cobalt compound particle in the mixture is reduced, the formation of above-mentioned conductive base can fully not carried out, and the utilance of active material can't increase.When concentration was higher than 14N, the viscosity of this alkaline aqueous solution can increase, and can't fully be penetrated into particle device inside, and abundant dissolved cobalt compound particle.

The use amount of alkaline aqueous solution is preferably, and with respect to 100 mass parts particles system, is 5～20 mass parts.

When being lower than 5 mass parts, whole amounts of the cobalt compound particle that contains in its very difficult dissolved particles equipment, thus can't improve the utilance of gained active material.In addition, use the capacity response rate after the storage of the battery that it manufactures also can't rise too much.

When amount surpassed 20 mass parts, particle device can be by granulation.Therefore, to be preferably with respect to 100 mass parts particle device be 10～15 mass parts to use amount.

3) manufacturing of the oxynickel hydroxide that covers with cobalt compound

The above-mentioned nickel hydroxide that covers with cobalt compound carries out oxidation by adding oxidant then by adding entry to form slurries, is oxidized to the oxynickel hydroxide that covers with cobalt compound.

In this operation, the nickel hydroxide particle that covers with cobalt compound and the ratio of water are preferably, and the nickel hydroxide particle that 100 mass parts cover with cobalt compound is to 5～30 mass parts water.As being used for oxidant of the present invention, can use the oxidant of clorox etc.

As clorox, can working concentration be 5～15%, 10～12% the aqueous solution more preferably.When concentration was lower than this scope, the viewpoint of the oxidation of the nickel hydroxide that personal cobalt compound covers is seen, and was improper.When concentration surpasses this scope,,, improper for the oxynickel hydroxide of the covering cobalt that obtains stable oxidizability because solution is all very unstable to air, heat and light etc.

Add the amount of oxidant of the nickel hydroxide particle slurries of above-mentioned covering cobalt, being preferably with respect to nickel hydroxide is 105～120 equivalents.

Thus, nickel hydroxide can convert oxynickel hydroxide to.

(anode mixture)

The common mixed cathode active material of positive pole of the present invention, electric conducting material, electrolyte, adhesive etc. are shaped it as the anode mixture metal pattern as anode mixture.

(manufacturing of anode mixture)

For example, use the regulation raw material, preparation has the compound nickel hydroxide particle of the high suboxide of cobalt in its surface.Add oxidant then, obtain to have the compound oxynickel hydroxide of the high suboxide of cobalt.

So the product of gained can turn out to be compound oxynickel hydroxide particle by XRD, and confirms that by the back titration method of iron ammonium sulfate/potassinm permanganate the roughly total amount of Ni is a trivalent.

In addition, by the Ni purity of EDTA titration or icp analysis mensuration compound oxynickel hydroxide at this moment, as the master data of following battery design.

The compound oxynickel hydroxide particle that has the high suboxide of cobalt in its surface in case of necessity, for example, as electric conducting material mixing carbon granule, further adds alkaline electrolyte as positive active material, and in case of necessity, mixed adhesive is as anode mixture again.

This anode mixture by pressurization form have its external diameter equal in fact the metal can internal diameter the hollow cylinder shape, obtain the anode mixture metal pattern.

In the anode mixture that is shaped, the positive active material particle is bonding with conducting material granule, and granule boundary is filled by electrolyte.

In the anode mixture metal pattern that is made of positive active material, collector body and electrolyte, the composition of each component is according to decisions such as fabrication strengths.

Because the design battery needs the data of closing the metal density of modes, so must measure.

In the present invention, in order further to improve anodal conductance, preferably, positive electrode (anode mixture) contains carbon granule.

As spendable carbon granule, can use the carbon black of the black or acetylene black of graphite, Ketjen etc.

The proportioning of carbon black is preferably and is not more than 15 quality %, and the ratio that is suitable for positive electrode active material confrontation carbon granule especially is 100: 3～10 (mass ratioes).

If carbon granule cooperation ratio is higher than this value, owing to the relative minimizing of active matter quality makes battery be unsuitable for high capacity.On the other hand, if carbon granule cooperation ratio is lower than this value, conductance is lower, and the height output property of battery makes us dissatisfied.

In the present invention, the carbon granule of above-mentioned cooperation, preferably selecting specific area is 1.0～30m ²/ g especially is 10～200m ²/ g, more preferably 0～100m ²The carbon granule of/g.

In these cases, specific area is lower than 1.0m ²During/g, particle diameter is excessive, and collection efficiency reduces, and can't obtain enough excellent high efficiency discharge.

If specific area surpasses 300m ²/ g, the easy oxidation of carbon granule meeting, the carbon ion that is produced can quicken self-discharge and cause the minimizing of discharge capacity.Therefore, be preferably in selection in the above-mentioned scope.

Under the situation of these carbon granules, use level is preferably 3～15 quality %, and more preferably 5～12 quality % are preferably 7～10 quality % again.

If the amount of the carbon granule that comprises in the anode mixture is lower than 3 quality %, be difficult to obtain abundant collection efficiency, and the high efficiency flash-over characteristic can reduce slightly.

If surpass 15 quality %,, can cause some reductions of battery capacity owing to can cause the minimizing of positive electrode active material quality.

Carbon granule can be the mixture of the carbon granule of different specific areas more than two kinds.In the case, carbon granule preferably 25～75 quality % specific areas be 1.0～30m ²The carbon granule of/g and 75～26 quality % specific areas are 30～300m ²The mixture of the carbon granule of/g.

If specific area is 30～300m ²The amount of the carbon granule of/g is lower than 25 quality %, and (specific area is 1.0～30m ²The amount of the carbon granule of/g surpasses 75 quality %), collection efficiency is understood some and is reduced, and can see that discharge capacity has the tendency of reduction.

On the other hand, if specific area is 30～300m ²The amount of the carbon granule of/g surpasses 75 quality %, and (specific area is 1.0～30m ²The amount of the carbon granule of/g is lower than 25 quality %), not only cause the increase of material cost, and self-discharge quickened by the carbon ion that the oxidation of carbon particulate produces, and can see that discharge capacity has the tendency of reduction.

That is, about the characteristic of the positive pole, electrode or the battery that constitute by anode mixture, it is very big that the specific area of carbon granule influences battery behavior, and the improvement of the combination of carbon granule and content and battery behavior has very dark relation.Therefore, suitably select and adjust the amount of the carbon granule that comprises in mixture as the carbon granule of the specific area of the carbon granule of electric conducting material, different specific areas, the anode mixture etc., not only can improve the high efficiency flash-over characteristic but also can promote the realization of high capacity.

In this embodiment, as the nickel hydroxide based compound of anode mixture main component be, for example the eutectic thing of the mixture of nickel hydroxide, oxynickel hydroxide, nickel hydroxide and oxynickel hydroxide (hybrid system) or they and zinc and/or cobalt.

About these nickel hydroxide based compound particles, generally can use average grain diameter is particle about 5～15 μ m.

In the above description, the carbon granule that comprises in the anode mixture can be the specific area substantial constant, also can be aforesaidly to form by the variety classes carbon granule that mixes different specific areas.

(anodal shaping)

Secondly, spherical oxynickel hydroxide particle according to the present invention is shaped as positive pole by following operation.

1) mixture of anode mixture component

Anode mixture can pass through hybrid conductive material, the adhesive as the anode mixture additive, lubricant and electrolyte etc. and get with positive active material.

Be used for reducing the material of the interior resistance of anode mixture as the electric conducting material of anode mixture component, use graphite usually.

In order to strengthen the shape hold facility when the shaping anode mixture and when being shaped and in battery, keep the shape hold facility, to use adhesive.Spendable adhesive is polyethylene, polypropylene, polytetrafluoroethylene etc.

Slippery between the metal pattern that improves anode mixture metal pattern and shaping usefulness improves productivity ratio, makes with lubricator.

Spendable lubricant is zinc stearate, calcium stearate, ethylenebisstearamide etc.In order to strengthen in the anode mixture ionic conductivity and to strengthen forming property, use electrolyte.

This electrolyte, preferred use with in order to the positive pole of maintenance battery and the identical electrolyte of electrolyte of the ionic conduction between negative pole.

Preferred electrolyte is the 40%KOH aqueous solution.

The mix proportion of the component of these anode mixtures is preferably, positive active material: electric conducting material: adhesive: lubricant: electrolyte is 90-92: 4-6: 0.05-0.5: 0.05-0.30: 4-6, is mass ratio.

These components are mixed by the blender of rotary blender or Heng Xieer blender etc.

2) roll processing

The anode mixture for preparing in the above-mentioned operation rolls the device compression by roller again, and for granulation increase packed density.This roller rolls device and supply anode mixture between two roller, and pressurization also increases packed density.Its compression stress is calculated divided by the roller width with the power that applies, and is preferably 0.5 * 10 ⁴～5 * 10 ⁴N/cm, more preferably 1.5 * 10 ⁴～3.5 * 10 ⁴N/cm.

This roller roll device can with radius square with the roller width improve treating capacity pro rata.

3) granulation processing

Roll anode mixture after the processing and be the form of compression blocks.

In order to prepare metal pattern, must be granulated into particle at once with it.

For this purpose, use the pelletizer of the two rollers that on its roller surface, have chimeric mutually teat to implement granulation processing.

The anode mixture of compression blocks form imports in the pelletizer, is broken into particle.

The diameter of gained particle is about tens μ m～1mm.

4) classification processing

The anode mixture particle of gained is by its grain size grading in the above-mentioned operation.In the present invention, by becoming the particle of 200～800 μ m, can form anode mixture metal pattern with high packed density.

Granulated powder less than 200 μ m is not suitable for, because need too many timing granulated powder when being shaped by metal pattern.

The granulated powder that surpasses 800 μ m also is not suitable for, because the quality of metal pattern can change when being shaped by metal pattern.

In batch process equipment, can set up a granulation apparatus, wherein sift out large diameter particle by granulation processing once more and re-use, and the particle of minor diameter is sent to roller and rolls the device procedure of processing and re-use by classification processing.

5) be shaped

The anode mixture particle of granulation in the above-mentioned operation re-uses metal pattern and is shaped as anodal formed body.

The counter-rotative type anode mixture has the hollow cylinder shape and has central axle.It is shaped by filling the anode mixture particle in the cylindrical metal mould with predetermined and drive male model and implement.Used forming pressure is preferably 0.5 * 10 ⁸～9.8 * 10 ⁸Pa.If forming pressure is lower than this scope, can't obtain the required packed density of anode mixture, be difficult to keep particle to contact with each other.Therefore, when finishing, battery can't provide the predetermined discharge amount.On the other hand, if forming pressure surpasses this scope, electrolyte is difficult to infiltrate in the anode mixture, and can reduce its utilance.

By using above-mentioned positive active material particle, because following reason, the susceptible of proof excellent effect comprises and improves shaping density, and improves the discharge capacity that uses its battery of making.

1) because particle forms spherulite, apply the pressure bigger than prior art even roll device from roller, crystal can not break yet.Therefore, even increase shaping density, utilance can not reduce yet, thereby significantly improves the actual discharge amount.

Traditionally, because particle has indefinite shape, shaping density can't increase.

In addition, when increasing shaping density, stress is concentrated serious, reduces utilance in the crystallization infringement of this part generation active material etc.Therefore, even increase shaping density, also can't improve the actual discharge amount.

2) because particle is spherical, so the space of filling between the crystal of back can be reduced.Therefore, shaping density is significantly improved.

3) even, also can obtain having the formed body of equivalent shaping density, so operation significantly improves because roller rolls the suitable low-pressure of device supply.

4) improve the productive rate that classification is processed.That is, productive rate is about 40% next time in the situation of manganese dioxide, improves approximately 60% according to a productive rate of oxynickel hydroxide of the present invention, has improved business efficiency.

5) improve formed body intensity.As a result, improve the shaping productive rate, breaking or crackedly wait minimizing much in the time of in anodal formed body imports jar also improves the dust operational environment and improves business efficiency.

(variation of anode mixture)

In en closed nickel-zinc primary battery according to the present invention, above-mentioned with the situation as the anode mixture of the positive active material of key component by nickel hydroxide and graphite under, preferably again stearic acid compound is mixed in the anode mixture.

In the case, stearic acid compound preferably with 0.05～0.5 quality %, especially go in the anode mixture by the mixed of 0.1～0.3 quality %.

If the proportioning of stearic acid compound surpasses this scope, can't substantially improve the shaping operation, simultaneously, the use level of its oppressive positive active material.Cause causing the shortcoming that battery capacity reduces slightly, cost rises, unfavorable from the viewpoint of the capacitance of last assemble, and the re-load discharge characteristic had adverse effect.

On the other hand, if stearic acid compound is lower than this scope, owing to add the minimizing of lubrification with the efficient of flowability of stearic acid compound particulate mixtures, the operation that is shaped reduces slightly, and productive rate also reduces slightly, and the property produced in batches is impaired.

The stearic acid compound that cooperates is preferably at least one material that is selected from zinc stearate and calcium stearate.

Because zinc stearate and calcium stearate are all excellent aspect lubrification, and can be by adding the purpose that the realization of being satisfied with is in a small amount wanted, so it can not cause the minimizing of battery discharge capacity.

In addition, about these additions, from comparing with existing alkaline Mn cell, can produce cheaply on the nickel-zinc cell with high efficiency flash-over characteristic and high power capacity in enormous quantities and see, the cooperation in this scope is well suited for.

Stearic acid compound preferably uses with powder type, and its average grain diameter preferable range is 1～10 μ m.

If average grain diameter is less than this scope, its difficult treatment covers the surface of particulate positive electrode mixture equably and must take time.

On the other hand, greater than this scope, stearic acid compound can't cover the surface of anode mixture particle fully, can't implement to improve the effect of lubrification as if average grain diameter.

The method of the formed body that the anode mixture that is mixed with as positive active material and stearic acid compound, the graphite made by above-mentioned nickel hydroxide based compound etc. constitutes; can enumerate following method as embodiment; this method comprises becomes the step of particle form containing nickel hydroxide based compound and graphite as the anode mixture mixture granulation of its key component, and stearic acid compound is added step in the particulate mixtures.

Fig. 2 is a flow chart of showing the method according to its sequence of steps.

(S1: do and stir)

In the oxynickel hydroxide powder of graphite powder adding, use multimixer to stir with dried alr mode as positive active material.

Mixing time is about five minutes.

In this operation, graphite adding rate ((quality of powdered graphite)/(quality of the quality+powdered graphite of active material)) is preferably 3～10 quality %, more preferably 5～8 quality %.If the content of graphite surpasses this scope, its formability, shaping operation are better, but discharge capacity can reduce, and does not reach the purpose of wanting.

If the content of graphite is lower than this scope, discharge capacity can increase really, but conductance can reduce in the positive active material, can reduce the re-load discharge characteristic.

(S2: the wet stirring)

100 mass parts are stirred the mixed-powder that obtains by doing, add electrolyte, use multimixer to stir by wet alr mode.

By this operation, but the powder by the dried anode mixture component that mixes combines and becomes shaped state.

The amount of the electrolyte that this operation is used with respect to 100 mass parts anode mixture components, is about 2～7 mass parts, and mixing time about five minutes was enough.

(S3: compression)

Secondly, the gained mixture rolls device by roller and is compressed into tabular.

At this moment, adjust the pressure etc. that roller rolls device, with the thickness limits of tabular compressed mixture in 1 μ m.

(S4: fragmentation)

Secondly, by the tabular compressed mixture of crusher in crushing.

(S5: screening)

Secondly, by the Automatic sieve extension set classification of 22～100 mesh, be about the anode mixture particle of 150～710 μ m with particle separation diameter.

(S6: mix and stir)

Secondly, the stearic acid compound powder of scheduled volume is added in the particulate mixtures of previous steps gained, mix and stir.About five minutes mixing mixing time is promptly enough.

(granular mixture)

By this step, can on particle surface, be stained with the granular mixture of stearic acid compound powder.

Then, this particulate positive electrode mixture is filled in the metal pattern, compression molding forms the anode mixture of a hollow cylinder form.Then, be assembled into battery by common battery fabrication schedule.

[negative material]

The used negative material of the present invention is with the negative material of negative electrode active material kirsite as its main component.Can use the used no mercury of known manganese dioxide-zinc primary cell, unleaded gel of zinc.

(manufacturing of cathode agent)

About negative pole, can use the used no mercury of the negative pole of known manganese dioxide-zinc primary cell, unleaded gel of zinc.In addition, negative pole gel density also need be measured so be preferably in the manufacturing battery in the past as the data of design battery.

Negative material is preferably maneuverable gel.Negative material becomes gel, can the gelation easily by add electrolyte and tackifier to negative electrode active material.

The used kirsite of the present invention can be as known mercurous, the not plumbous kirsite of mercury-free zinc alloy.

Particularly, the kirsite that contains 0.06 quality % indium, 0.014 quality % bismuth and 0.0035 quality % aluminium is more suitable, because the effect that prevents that hydrogen from producing is arranged.

Indium and bismuth can be particularly suitable for improving flash-over characteristic.

Use kirsite to replace pure zinc and be that as the reason of negative pole operative material it postpones in alkaline electrolyte the speed of dissolving voluntarily, when finishing, can prevent that hydrogen is created in the inboard of battery, thereby prevent the accident that liquid is sewed to airtight shape battery product.

Kirsite is preferably powder type to increase surface area and to tackle heavy-current discharge.

The average grain diameter of the kirsite that the present invention is used is preferably 100～350 μ m.

If average grain diameter is less than 100 μ m, make the even difficulty of mixing of electrolyte and gel, simultaneously, activating surface easily causes unstable acting on as oxidized reliability.

If average grain diameter surpasses 350 μ m, the minimizing of surface area can make and tackle the heavy-current discharge difficulty.

In addition, if average grain diameter during less than this scope, is operated when material is difficult in assemble, be difficult to mixed electrolytic solution and gel equably, and activating surface is easily oxidized and unstable.

The used tackifier of the present invention can be polyvinyl alcohol, polyacrylate, CMC or alginic acid.

Polyacrylic acid is preferred especially, because the anti-chemical excellence of its antagonism strong acid.

[electrolyte]

The used electrolyte of the present invention is preferably and uses basic salt as with potassium hydroxide or the NaOH aqueous solution as solute.Preferably use potassium hydroxide.

In the present invention, basic salt such as potassium hydroxide are dissolved in the water to form electrolyte, add zinc compound but be preferably to electrolyte again.

About zinc compound, just like the compound of zinc oxide and zinc hydroxide etc.Wherein, preferred especially with zinc oxide.

As electrolyte, use the reason of the alkaline aqueous solution that contains zinc compound at least to be, the voluntarily dissolving of kirsite in alkaline aqueous solution is much lower than the acidic electrolysis bath person, and by solving zinc compound such as zinc oxide and produce zinc ion in advance, the voluntarily dissolving of kirsite in alkaline aqueous solution further suppressed.

The optimum concentration range of electrolyte is 7～11 mol, to obtain high conductivity.

Therefore, in the present invention,, can realize excellent high-capacity battery by in above-mentioned nickel-zinc primary battery, making active material and electrolyte optimization.

[manufacture method of battery]

Below, according to the manufacture method of its operation detailed description according to en closed nickel-zinc primary battery of the present invention.

[processing of anodal box]

Preparation to the metallic plate that is used in iron-based material electroplating nickel on surface preparation draw acquisition, according to the anodal box of the cylindrical shape of JIS standard LR6 type (size AA) battery.

By at first on the inner wall surface of anodal box, spraying the coating that covers the about 20 quality % graphite powders that contain dispersion, then by the evaporating solvent dry paint, on the interior ancient piece of jade, round, flat and with a hole in its centre surface of anodal box, form the layer of graphite system, can reduce the interior resistance of battery.

(formation of anode mixture (positive pole))

Thereafter, preparation is combined with the compound nickel hydroxide particle of the high suboxide of cobalt on the specified feedstock surface, add oxidant again, makes the compound oxynickel hydroxide that is combined with the high suboxide of cobalt.

So the product of gained can be identified by XRD and turn out to be compound oxynickel hydroxide particle, and confirms that by the back titration of ferrous ammonium sulfate/potassinm permanganate all Ni amounts all become trivalent in fact.

Secondly, mix and stir the powder of anodal action material and the powder of Delanium, this Delanium is as conductive agent, and provides formability and to the release property of metal pattern.

, use the metal pattern of with JIS standard LR6 type (size AA) battery suitable shaping anode mixture, form the anode mixture of hollow circle tube by compression molding thereafter.

(formation of negative pole)

Under reduced pressure by stirring and mix the potassium hydroxide aqueous solution (electrolyte) and the gel of mercury-free zinc alloy powder, adding zinc oxide, preparation gel of zinc negative pole.

(formation of dividing plate)

Also bonding by the nonwoven fabrics that fibers such as coiling polyvinyl resin constitute by the hot melt part, obtain a cylinder.

In addition, go out a plectane from for example polyvinyl resin sheet, this plectane is by the end of hot melt adhesive to this cylinder, to obtain having the cylindrical shape dividing plate of bottom.

(assembling of alkaline battery)

Cylindrical shape anode mixture, negative electrode gel and the dividing plate of so preparation are assemblied in and the inboard of JIS standard LR6 type battery with the anodal box of suitable double as positive terminal, to constitute the alkaline battery of size AA.

Be characterised in that according to the manufacture method of this embodiment the environment of making behind the positive active material by control can prevent its deterioration.

The high suboxide of nickel is a positive active material, is made of the oxynickel hydroxide as its key component.Yet this compound is to moisture allergy, and when being exposed to the environment that contains moisture as if the high suboxide of nickel, it can cause the change of deoxidation and nickel hydroxide quality with the moisture reciprocation.

When being reduced into nickel hydroxide fully, nickel series compounds no longer produces electric power, and can't constitute battery.

Therefore, when using the high suboxide of nickel as the positive active material assemble, the high suboxide of nickel preferably leaves in the dry air.

Yet, need a very big equipment in order to remove moisture fully from air, and it can worsen the operation in the battery manufacturing process.

Therefore, suppress between high suboxide of nickel and moisture interactive means from the dewatered means of air and further investigate, be accomplished method of the present invention use replacing.

That is, the method is by handling its storage condition, makes under its environment that can not be exposed to 30 ℃ or higher temperature before the step of using the high suboxide assemble of nickel, can prevent the change of nickel high order oxide quality.

Equipment can be finished by cooling off the room temperature that stores and control the place of positive active material for this purpose.

For this purpose, can use the typical apparatus of air conditioning.

The equipment that can reduce humidity when regulating temperature then more preferably.

(variation of cell manufacturing method)

Secondly, a kind of method for optimizing of making according to en closed nickel-zinc primary battery of the present invention is described.

The method is characterised in that the battery assembling back enforcement high-temperature aging in the manufacturing process of battery.

This high-temperature aging is preferably in 40～80 ℃ and continues 24～72 hours down.

When temperature is θ [℃], the time is the t[time], can be by (θ: t)=(40-80: 24-72) timeliness is implemented in the combination of scope, can easily adjust OCV (OCV can be reduced) to the en closed nickel-zinc primary battery after the assembling.

Adjust the typical method of OCV, existing for resembling the button shaped manganese lithium primary battery any permanent resistor of direct connection with the generation partial discharge.

Yet the method needs as discharge cell and the equipment that prevents the voltage control apparatus etc. of over-discharge can.

That is, the cost of this equipment increases the cost of final product.

The general reason of the voltage adjustment of the direct-connected partial discharge of permanent resistor of using comprises: (1) is used and is difficult for the active material of self-discharge as negative pole, and (2) no matter whether it is aqueous solution equipment use to be difficult for the active material of self-discharge as positive pole.

About above-mentioned (1), can enumerate the lithium of non-aqueous solution system and the zinc of water solution system etc. and be negative electrode active material.

When the lithium of non-aqueous solution system during, form the coating of lithium carbonate compound in its surface and be difficult to self-discharge with for example propene carbonate (PC) combination.

When the zinc of water solution system makes up with for example potassium hydroxide (KOH solution), form the coating of zinc hydroxide compound, be difficult to self-discharge.

About above-mentioned (2), use than the more electronegative active material of the oxidation-reduction potential of electrolyte usually.

For example, can enumerate the manganese dioxide of water solution system and the manganese dioxide of water solution system is example.

They can be respectively and combinations such as for example PC or the electrolytic aqueous solution such as the KOH aqueous solution.Yet, because than the oxidation-reduction potential of electrolyte elecrtonegativity more, electrochemistry self-discharge can not take place.

Therefore, by implementing directly to connect the current potential that the partial discharge of carrying out can reduce negative or positive electrode effectively by permanent resistor.

The nickel-zinc primary battery of exploitation such as the inventor, anodal oxynickel hydroxide, the electrolyte of using uses with the alkaline electrolyte of KOH as its key component.

Oxynickel hydroxide can carry out self-discharge than the oxidation-reduction potential of electrolyte (water) elecrtonegativity more.

Consider in this, the invention provides a kind of factor and implement the method that OCV is adjusted in suitable self-discharge that having thus need not optional equipment such as the effect of permanent resistor discharge and so on by temperature θ and time t.

Secondly, illustrate that a kind of high suboxide of nickel that uses is as containing zinc and cobalt or the two is the manufacture method of the oxynickel hydroxide of eutectic form as the en closed nickel-zinc primary battery of positive active material.

The method is characterised in that, the high suboxide of nickel is stored in 30 ℃ or following temperature before assemble, in the manufacturing of en closed nickel-zinc primary battery, control the anodal high suboxide of nickel reliably with a simple device, to prevent that capacity reduces because of self-discharge in the manufacturing process of battery.

Above-mentioned positive active material can be the compound oxynickel hydroxide that zinc and cobalt or the two are the eutectic form that contains that is covered by cobalt high order oxide skin(coating).

[embodiment]

Secondly, based on embodiment the present invention is described.

(embodiment 1～5 and comparative example 1～4)

By in atmosphere, the nickel hydroxide particle that is doped with 5% zinc and 1% cobalt to 100 mass parts adds 7 mass parts Co (OH) ₂, to stir simultaneously with microwave heating, and spray 15 mass parts 10NNaOH, preparation has the compound nickel hydroxide particle of the high suboxide of cobalt in its surface.Further clorox is added in this system with accelerating oxidation, with the compound oxynickel hydroxide that obtains to mix with the high suboxide of cobalt.

So the product of gained is identified by XRD and is turned out to be compound oxynickel hydroxide particle, and confirms that by the back titration of iron ammonium sulfate/potassinm permanganate all Ni amounts all become trivalent in fact.

In addition, Ci Shi compound oxynickel hydroxide Ni purity is determined as 54% by EDTA titration and icp analysis.

In the positive active material that obtains by this method, add carbon and electrolyte, be configured as anode mixture.

Consider the fabrication strength of anode mixture etc., each of anode mixture shows the amount mixing of mass ratio below composition.

That is compound oxynickel hydroxide: carbon: 12N KOH=100: 6: 5, the density that is shaped this moment was 3.22g/cm ³

About negative pole, no mercury, the no hard lead of the negative pole by using known manganese dioxide-zinc primary cell prepare cathode agent.The gel of zinc composition of cathode agent is as follows.

Zinc: absorbent binder: 12N KOH=100: 1.5: 55

This moment, the density of gel of zinc was 2.70g/cm ³

Used electrolyte is the 12N KOH aqueous solution.

Measure the anode mixture that so obtains and the quality of negative pole gel, be packed in one jar, the ratio of anodal theoretical capacity is poured into electrolyte with the electrolyte of 1.3ml/Ah.Then, the formation shown in embodiment 1～3 table 1 is with the airtight metallic plate/negative pole top with collector body/gas release hole of incorporate airtight member, to obtain AA size zinc nickel primary battery shown in Figure 1.

Except the electrolyte ratio with respect to anodal theoretical capacity be adjusted into 1.7,1.6,1.0 and 0.8ml/Ah, to make other battery of embodiment 4,5 and comparative example 3,4 with embodiment 3 same way as.

The value of the anodal theoretical capacity of made battery, negative pole theoretical capacity, negative pole/anodal theoretical capacity ratio all is shown in table 1.

Each battery of finishing is implemented the constant-current discharge that 150mA 1.0V blocks under 20 ℃ of atmosphere after exposure made it activation in three days under 20 ℃ of atmosphere.

Thereafter, the gained discharge capacity by positive pole calculates anodal utilance divided by theoretical capacity.

It the results are shown in table 1.

In addition, except the ratio of the used negative pole/anodal theoretical capacity of existing Ni-MH secondary battery becomes 2 and 3, prepare the battery of comparative example 1 and 2 in the mode identical with embodiment 4.

By table 1 susceptible of proof, be 2～3 because the design of the secondary cell of comparative example 1 and 2 needs Capacity Ratio, so it needs the theoretical capacity of positive pole shown in the table 1 and negative pole, in the battery tank body that is stored in limited bulk, battery capacity is 1500～1900mAh.

On the other hand, under the situation of primary cell according to the present invention design, because Capacity Ratio can hang down to 1.0～1.6, so the increase of susceptible of proof capacity becomes possibility to the battery of comparative example the most about 70%.

As shown in Table 1, relevant with respect to the electrolyte ratio of anodal theoretical capacity with the anodal utilance of the capacity regulating utmost point, and the value of 1.0～1.6ml/Ah is suitable.In surpassing the scope (1.7ml/Ah) of 1.6ml/Ah, anodal utilance meets, and can become VOLUME LOSS and add the electrolyte that surpasses this scope in the limited internal volume of battery.

In being lower than the scope of 1.0ml/Ah (0.8ml/Ah), the rapid minimizing of anodal utilance, obviously unactual.

Suppose that it is because electrolyte is not enough and proton can't be well-dispersed in the anodal oxynickel hydroxide.

(embodiment 6～8 and comparative example 5)

Except the battery of the composition of electrolyte and the embodiment 4 of conductance from table 1 become in the table 2 shown in the embodiment 6～8, to make two batteries of each embodiment with embodiment 4 same way as.

For the purpose of comparison, manufacturing has the battery that conductance is 0.16S/cm (comparative example 5).

Be similar to embodiment 1～5, these batteries expose three days and make it to activity in 20 ℃ of atmosphere after, be divided into two groups.One group battery carries out the constant-current discharge that 150mA 1.0V blocks in 20 ℃ of atmosphere, the battery of another group was then exposing for two weeks in 45 ℃ atmosphere, similarly carries out the constant-current discharge of 150mA again in 20 ℃ of atmosphere.Likening to of both utilances is the capacity sustainment rate after two weeks of exposure in 45 ℃ of atmosphere.

It the results are shown in table 2.

Under the situation of commercially available typical AA size manganese dioxide-zinc primary cell, capacity confirms that electric current is the 20mA discharge, and intermediate current is the 150mA electric current.

That is, by the 150mA discharge, manganese dioxide-zinc primary cell can qualitatively judge the comparison of discharge rate characteristic.

As shown in Table 2, conductance is relevant with anodal utilance, can't obtain, unless the current potential conductivity of abundant anodal utilance electrolyte be 0.2S/cm or more than.

Also known, add the electrolyte of LiOH and NaOH (or only containing NaOH), higher than the capacity sustainment rate of the electrolyte of embodiment 4 being seen only KOH.

Yet, when known ratio as if LiOH or NaOH rises in electrolyte,,, must decide according to application target and the characteristic of wanting so it must suitably be selected and use because it reduces conductance and anodal utilance.

Therefore, preferably use conductance to be not less than 0.2S/cm, use KOH as basis and add NaOH with LiOH at least one system, or use NaOH not reach the NaOH of 12N and add the system of LiOH as basis or use.

In addition, for by using NaOH or LiOH to make conductance be not less than 0.2S/cm, can use as 9～11N to low concentration from 12N or 12N+1N=13N by the whole basic salt concentration shown in the dilution table 2.

In addition, for the purpose of comparison, buy commercially available AA size manganese dioxide-zinc primary cell (being commonly referred to " alkaline battery "), its discharge capacity blocks the discharge assessment by similar 150mA 1.0V.Thereafter, it is decomposed to determine the amount of manganese dioxide in the battery, is 70% from the ratio assessment utilance to theoretical capacity.

Embodiment 4,6 and 7 battery have the utilance that surpasses commercially available alkaline battery in the table 2, and this battery system is verified superior aspect the discharge rate characteristic.

(embodiment 9～13)

Except four kinds of metal oxides or the metal fluoride that adds 0.4 mass parts, that is, and Y ₂O ₃, Er ₂O ₃, Yb ₂O ₃And CaF ₂In addition, with table 1 in embodiment 4 same way as make battery.

Identical in aging condition, the anodal utilance of mensuration finished after battery is made with the mode and the said method of capacity sustainment rate.

It the results are shown in table 3.

Result from the result of table 3 and the embodiment 4 corresponding with table 2 can confirm, it is effective to improving the capacity sustainment rate that the fluoride of the oxide of Y, Er and Yb and Ca is added its anodal battery.

Also the embodiment of verification table 3 has the gratifying anodal utilance that is equivalent to embodiment 4.

Especially, positive pole adds Y ₂O ₃The system and the capacity sustainment rate of the combination of 12N KOH+1N NaOH verified very excellent.

By adding Y, Er and the oxide of Yb or the fluoride of Ca at positive pole, suitably adjust electrolyte not only only contain the system of KOH and also add NaOH or whole concentration of the system of LiOH to keep the conductance more than the 0.2S/cm, anodal utilance can be do not reduced, the capacity sustainment rate when storing can be improved.

Though embodiment shown here is essentially the AA size, it is not subject to this size, can be applicable to various sizes.

In addition, though embodiment uses the compound oxynickel hydroxide displaying that is covered positive active material by the high order cobalt compound, even use yet susceptible of proof same effect of oxynickel hydroxide, positive active material is not subject to this.

(embodiment 14～19 and comparative example 6 and 7)

(anodal preparation)

By the oxynickel hydroxide powder that 90 quality % are covered by cobalt hydroxide, mix 5.4 quality % graphite powders and last 10 minutes, the aqueous solution that contains 40% concentration hydrogen potassium oxide that adds 4.6 quality % then gets mixed-powder with its mixing 30 minutes in multimixer.

Is the hollow cylinder form of external diameter 13.3mm, internal diameter 9.0mm and height 13.7mm with it by compression molding, obtains the anode mixture pill.

(preparation of negative pole)

To 64.58 quality % contain 0.01 quality %In, 0.01 quality %Bi and 0.003 quality %Al, average grain diameter is the Zinc alloy powder of 100～300 μ m, add 0.381 quality % polyacrylic acid as gelling agent, and in multimixer, stir and evenly mixed in 5 minutes.

Then,, add 0.0006 quality % tetrabutylammonium hydroxide, it is stirred 10 minutes with abundant dispersion in the containing 35 quality % concentration hydrogen potassium oxides and contain in the aqueous solution of zinc oxide of 3.5 quality % dissolving of 35 quality %.Thereafter, the mixture that adds Zinc alloy powder is gradually gone through 4 minutes, stirs under the decompression that is no more than 150mm Hg and mixing, stirs under the decompression state that is not higher than 10mm Hg, to obtain even negative electrode gel again.

(assembling of electrode)

Use the negative electrode gel that obtains in the above described manner, installation diagram 1 illustrated dimension AA alkaline battery (embodiment 14).

For each LR6 of assembling, after two days, in 20 ℃ of atmosphere, implement the constant-current discharge of 150mA and 1000mA in timeliness,

It the results are shown in table 4.

Except the quality of anode mixture 2, that is, anodal quality is adjusted into beyond the 9.3g shown in the table 1,9.6g, 10.0g, 10.3g, 10.6g, 8.7g and the 10.9g, with with embodiment 14 same way as manufacturing dimension AA alkaline batteries (embodiment 15,16,17,18,19 with comparative example 6 and 7).

To measure the battery behavior of these batteries with embodiment 14 same way as.

It the results are shown in table 4.

As shown in table 4, the ratio of the volume that non-solid part occupies in positive pole and the volume of positive active material is 0.52, exceeds under the situation of comparative example 6 of the scope of the invention, and the discharge capacity of 1000mA and utilance are quite low.

At this moment, because solid particle, that is, reduce the contact between oxynickel hydroxide particle and graphite granule, causes the conductivity of whole positive pole to reduce, thereby high efficiency flash-over characteristic deterioration.

In addition, the ratio of the volume that non-solid part occupies in positive pole and the volume of positive active material is 0.18, and in the comparative example 7 less than the scope of the invention, the discharge capacity of 1000mA and utilance are quite low.

At this moment, because moisture is local not enough in the required electrolyte of the exoelectrical reaction of oxynickel hydroxide, can stop reaction and deterioration high efficiency flash-over characteristic.

In addition, in anode mixture, the ratio of the volume that non-solid part occupies is 32 volume %, exceeds under the situation of comparative example 6 of the scope of the invention, and the discharge capacity of 150mA and utilance are quite low.

At this moment, because owing to be filled in the deterioration of the fabrication strength of the positive pole in the metal can, active material seriously comes off and reduces discharge capacity in follow-up fabrication schedule.

In addition, in anode mixture, the ratio of the volume that non-solid part occupies is 14 volume %, and under the situation less than the comparative example 7 of the scope of the invention, the discharge capacity of 150mA and utilance are quite low.

At this moment, because owing to be filled in the possibility of breaking of the positive pole in the metal can, the current collection performance of whole positive pole is understood deterioration and is reduced discharge capacity.

(embodiment 20～22 and comparative example 8)

As shown in table 5, except for 90 quality % oxynickel hydroxide powder, graphite powder is adjusted into 0 quality %, 2.7 quality %, 8.1 quality % and 10.8 quality %, the potassium hydroxide aqueous solution of the 40 quality % that add is adjusted into beyond 2.3 quality %, 3.5 quality %, 5.8 quality % and the 6.9 quality %, with embodiment 17 same way as preparation size AA alkaline batteries ( embodiment 20,21,22 and comparative example 8).

These batteries are also to carry out the mensuration of battery behavior with embodiment 14 same way as.

It the results are shown in table 5.

As shown in table 5, under the situation of content of graphite greater than the comparative example 8 of 10 quality %, discharge capacity and the utilance of 150mA all reduce in anode mixture.

At this moment, because the amount of active material itself reduces, thus the discharge capacity minimizing, and, cause discharge capacity to reduce by the carbonic acid ion acceleration self-discharge that graphite oxidation produces.

(embodiment 23,24 and comparative example 9)

Cover the oxynickel hydroxide except covering to replace with metallic nickel and metallic cobalt respectively, to prepare the size AA alkaline battery of embodiment 23,24 with embodiment 17 same way as with cobalt hydroxide.Cover the cobalt hydroxide except using unlapped oxynickel hydroxide to replace, to prepare another size AA alkaline battery of comparative example 9 with embodiment 17 same way as with cobalt hydroxide.

These batteries are also to carry out the mensuration of battery behavior with embodiment 1 same way as.

It the results are shown in table 6.

As shown in table 6, oxynickel hydroxide is compared with uncoated comparative example 9 with the embodiment 17,23 and 24 that cobalt hydroxide, metallic nickel and metallic cobalt cover respectively, and the discharge capacity of 150mA and 1000mA and utilance improve.

At this moment, because the surface of oxynickel hydroxide covers by the material with high electrical conductivity,, can improve discharge capacity and high efficiency flash-over characteristic so the conductance of whole positive pole can strengthen.

(embodiment 25)

Anodal preparation

In the oxynickel hydroxide particle (have 235 ℃ of endothermic peaks, resistivity is 10 Ω cm) that 90 mass parts are covered by the high order cobalt of the means gained of above-mentioned preparation positive active material, add 5.4 mass parts graphite powders, with its stirring and mixed 10 minutes.

Then, add 40 quality % potassium hydroxide aqueous solutions of 4.6 mass parts, in the multimixer container, mix 30 minutes to obtain mixture.

Thereafter, this mixture is configured as the hollow cylinder body of external diameter 13.3mm, internal diameter 9.0mm and height (length) 13.7mm by compression forming method.

The preparation of negative pole

Contain in the Zinc alloy powder that 0.01 mass parts indium, 0.01 mass parts bismuth and 0.03 mass parts aluminium and average grain diameter are 100～300 μ m in 64.58 mass parts and to add 0.381 mass parts polyacrylic acid (gelling agent), the multimixer container for stirring with mix 5 minutes with the thing that is uniformly mixed.

On the other hand, in being dissolved with 35 quality % potassium hydroxide aqueous solutions of 3.5 quality % zinc oxide, 35 mass parts add 0.0006 mass parts tetrabutylammonium hydroxide, with its stirring and mix 10 minutes with abundant dispersion.

, the mixture of above-mentioned Zinc alloy powder system gradually added this disperse system go through 4 minute, be not higher than 200 * 10 thereafter ⁵Under the decompression of Pa (150mm Hg) with its stirring and mixing.Be not higher than 13.3 * 10 again ⁵With its stirring and mixed 5 minutes, obtain a negative electrode gel of evenly forming system under the decompression of Pa (10mm Hg).

The assembling of battery

Secondly, use the anode mixture pill and the negative electrode gel of so preparation, by the size AA nickel-zinc primary battery shown in the schematic section of routine techniques installation diagram 1.

(embodiment 26～32 and comparative example 10 and 11)

Except as positive active material, use apparatus to have beyond the oxynickel hydroxide that the high order cobalt compound of physical characteristic as shown in table 7 (endotherm peak temperature and resistivity) covers, with embodiment 7 the same terms under preparation size AA nickel-zinc primary battery.

Table 7 is showed the physical characteristic that comprises embodiment 25.

To each nickel-zinc cell of above-mentioned assembling, in 25 ℃ of following timeliness of temperature after about 48 hours, in being 20 ℃ atmosphere, temperature implements the constant-current discharge of 150mA or 1000mA, from discharge capacity assessment utilance with respect to the theoretical capacity of positive active material.It the results are shown in table 8.

From table 8 as can be known, use is by having the sample (embodiment) that endotherm peak temperature is the positive electrode made of oxynickel hydroxide that 200～260 ℃ high order cobalt compound covers in differential thermal analysis, sample (comparative example) discharge capacity by having the oxynickel hydroxide that the high order cobalt compounds of endotherm peak temperature beyond being 200～260 ℃ cover is bigger than using.In addition, embodiment confirms to have the high efficiency discharge capacity along with resistivity increases and the tendency of minimizing.

To embodiment 25 and 30 nickel-zinc primary batteries that adopted, the utilance when discharge with 150mAh after 60 ℃ of temperature are placed 20 hours down is 100% as if embodiment 25, then embodiment 30 be 95%.Suppose that this difference is, because self-discharge is suppressed because of the γ oxynickel hydroxide exists.

(embodiment 33)

Anodal preparation

To 90 mass parts by forming in its surface in the high order cobalt layer compound nickel hydroxide particle in its surface that the means of above-mentioned preparation positive active material obtain, adding 5.4 mass parts specific areas is 3.4m ²The graphite powder of/g and 0.1 mass parts polyvinyl resin be as adhesive, stirs and mixed 10 minutes.

, add 40 quality % potassium hydroxide aqueous solutions of 4.6 mass parts, mixed 30 minutes in the multimixer container, obtain mixture thereafter.

Subsequently, this mixture is configured as the hollow cylinder body of external diameter 13.3mm, internal diameter 9.0mm and height (length) 13.7mm by compression forming method.

The preparation of negative pole

Contain in the Zinc alloy powder that 0.01 mass parts indium, 0.01 mass parts bismuth and 0.03 mass parts aluminium and average grain diameter are 100～300 μ m in 64.58 mass parts and to add 0.381 mass parts polyacrylic acid (gelling agent), the multimixer container for stirring with mix 5 minutes with the thing that is uniformly mixed.

On the other hand, in being dissolved with 35 quality % potassium hydroxide aqueous solutions of 3.5 quality % zinc oxide, 35 mass parts add 0.0006 mass parts tetrabutylammonium hydroxide, with its stirring and mix 10 minutes with abundant dispersion.

, the mixture of above-mentioned Zinc alloy powder system gradually added this disperse system go through 4 minute, be not higher than 200 * 10 thereafter ⁵Under the decompression of Pa (150mm Hg) with its stirring and mixing.Be not higher than 13.3 * 10 again ⁵With its stirring and mixed 5 minutes, obtain a negative electrode gel of evenly forming system under the decompression of Pa (10mm Hg).

The assembling of battery

Secondly, use the anode mixture pill and the negative electrode gel of so preparation, by the size AA nickel-zinc primary battery shown in the schematic section of routine techniques installation diagram 1.

(embodiment 34～39 and comparative example 12 and 13)

The carbon granule that has a specific area as shown in table 9 except use is as the graphite granule that is contained in the anode mixture 2, with embodiment 33 the same terms under preparation size AA Alkaline Zinc primary cell.

Table 9 is showed the occasion of embodiment 33.

Each alkaline zinc cell to above-mentioned assembling, in timeliness after about 48 hours, in being 20 ℃ atmosphere, temperature implements the constant-current discharge of 150mA or 1000mA, from theoretical discharge capacity assessment utilance with respect to constant-current discharge amount, each constant-current discharge amount and the positive active material of theoretical discharge capacity.It the results are shown in table 10.

From table 10 as can be known, the carbon granule specific area that contains of anode mixture 2 is 1.0～300m ²(each embodiment) all shows discharge capacity and the utilance of satisfied 150mA and 1000mA during/g.

On the other hand, 0.9m ²The sample of/g (comparative example 12) is showed low 1000mA discharge capacity and utilance.

Suppose that its reason is a solid particle, that is, the contact between oxynickel hydroxide particle and carbon granule can be reduced, and this causes the minimizing of whole anodal conductance and the deterioration of high efficiency flash-over characteristic.

On the other hand, the carbon granule specific area that contains at anode mixture is 320m ²The sample of/g (comparative example 2) is showed low 150mA discharge capacity and utilance.

Suppose that its reason is that the oxidation reaction of carbon granule can be quickened, the carbonic ester ion that is produced by oxidation can quicken self-discharge, by to reduce discharge capacity.

(embodiment 40～42 and comparative example 14 and 15)

Except as the carbon granule that is contained in the anode mixture 2, specific area is 30m ²Beyond the proportion of composing of the graphite granule of/g (quality %) is as shown in table 11, with embodiment 33 the same terms under preparation size AA Alkaline Zinc primary cell.

Each alkaline zinc cell to above-mentioned assembling, in timeliness after about 48 hours, in being 20 ℃ atmosphere, temperature implements the constant-current discharge of 150mA or 1000mA, from theoretical discharge capacity assessment utilance with respect to constant-current discharge amount, each constant-current discharge amount and the positive active material of theoretical discharge capacity.It the results are shown in table 12.

From table 12 as can be known, use the sample (comparative example 14) of the anode mixture 2 contain 2.7 quality % carbon granules, containing carbon granule with use is that the sample of the anode mixture of 3～15 quality % is compared, and shows lower 150mA and 1000mA discharge capacity and utilance.

Suppose that its reason is the required carbon granule amount generation shortage of electric current collection of oxynickel hydroxide particle, and it causes the minimizing of utilance.

Use contains low 15mA discharge capacity and the poor efficiency of sample (comparative example 15) displaying that carbon granule surpasses the anode mixture 2 of 15 quality %.

Suppose that its reason is the minimizing that the minimizing of the particles filled amount of oxynickel hydroxide causes discharge capacity, the carbonic acid ion that is produced by the oxidation of graphite can quicken self-discharge and reduce discharge capacity.

(embodiment 43～49)

The carbon granules that are contained in the anode mixture 2 except conduct are that specific area is 14m ²The granular graphite of/g and specific area are 270m ²The granular graphite of/g has the mixed stocker of mixing ratio of table 11 and the portfolio ratio of these mixed stockers is adjusted into beyond the 8.1 quality %, with embodiment 33 the same terms under preparation size AA Alkaline Zinc primary cell.

Table 13 is showed the occasion of embodiment 35 and 39.

Alkaline zinc cell to each assembling, in timeliness after about 48 hours, in being 20 ℃ atmosphere, temperature implements the constant-current discharge of 150mA or 1000mA, from theoretical discharge capacity assessment utilance with respect to constant-current discharge amount, each constant-current discharge amount and the positive active material of theoretical discharge capacity.It the results are shown in table 14.

As shown in Table 14, the discharge capacity of 150mA and 1000mA and utilance are along with specific area in the carbon granule that comprises in the anode mixture is 14m ²The carbon granule of/g and specific area are 270m ²Mixing ratio between the granular graphite of/g and difference.

That is be that specific area is 14m, at nearly all carbon granule ²In the sample of the carbon granule of/g (embodiment 35 and 43), because it is little to have the carbon granule amount of low particle size, shortage takes place in the amount of carbon granule around the positive active material, and reduces the electric current collection efficient of positive active material particle.

On the other hand, be that specific area is 270m at nearly all carbon granule ²In the sample of the carbon granule of/g (embodiment 39 and 49), the discharge capacity of 150mA and 1000mA and utilance are all low.

Suppose that its reason is, the carbonic acid ion that is produced by the oxidation of graphite can quicken self-discharge and reduce discharge capacity.

(embodiment 50)

As active material, the adding graphite powder also stirred 5 minutes in general mixer with the oxynickel hydroxide powder after covering processing with 5 quality % cobalt hydroxides.

Add graphite ratio be 5%.

The aqueous solution that adds 5 mass parts, 40 quality % concentration of potassium hydroxide in the mixed-powder of 100 mass parts gained like this stirred 5 minutes by wet alr mode in the multimixer.

Then, the gained mixture rolls device with roller and is compressed into the plate of thickness less than 1mm.

Subsequently, tabular compressed mixture is broken also by the automatic screening machine graded particie of 22～100 mesh with destroyer, obtains to have the particulate mixtures that particle diameter is 150～710 μ m.

Then, in the particulate mixtures of gained like this, add the zinc stearate powder, stir to obtain to contain the particulate mixtures of the zinc stearate powder that sticks on the particle surface.

The amount of the zinc stearate powder that adds is 0.1 quality % with respect to the quality of particulate mixtures.

(embodiment 51)

Except using the calcium stearate powder to replace the zinc stearate powder as the stearic acid compound, to prepare particulate mixtures with embodiment 1 same way as.

(embodiment 52)

Except replacing the oxynickel hydroxide powder that covers processing with 5 quality % cobalt hydroxides, beyond positive active material, to prepare particulate mixtures with embodiment 50 same way as with the oxynickel hydroxide powder that covers after processing with 5 quality % metallic nickels.

(embodiment 53)

Except replacing with the oxynickel hydroxide powder after the 5 quality % cobalt hydroxides covering processing, beyond positive active material, to prepare particulate mixtures with embodiment 50 same way as with the oxynickel hydroxide powder that covers with 5 quality % metallic cobalts after processing.

(comparative example 16)

Except not adding the calcium stearate powder, to prepare particulate mixtures with embodiment 50 same way as.

(manufacturing of battery)

Five kinds of particulate mixtures of above-mentioned gained form the hollow cylinder body of the size (size AA) of JIS standard LR6 type by using the tablet press machine compression molding.

Shaping density is 3.20g/cm ³

Be compressed at three kinds of particulate mixtures and form that to have shaping density be 3.20g/cm ³The operation of hollow cylinder body in, for release property relatively, the situation of the creak that produces because of friction is showed in table 15.

According to the result of table 15, do not use the comparative example 16 of stearic acid compound when the compression molding of hollow cylinder body, to produce creak, make a large amount of production difficulties.The embodiment 50～53 of use stearic acid compound has showed the effect of stearic acid compound lubrification.

Even under the situation of the comparative example that does not use stearic acid compound, creak also can be removed by the graphite ratio that adds is increased to about 10%.Even so, consider the capacitance after the assemble in the end, poorer than embodiment 50～53.

Subsequently, be 3.20g/cm for five kinds of particulate mixtures of comparison are processed into shaping density ³The formability of formed body of hollow circle tube bodily form formula, the anti-breakdown strength of each formed body is measured with the Rheometer CRX200D (n=100) that the San Kagaku of manufacturer makes.

Measurement result is showed in table 16 (mean value of n-100).

Shown in table 16, the intensity of embodiment 50～53 is about 1.5 times of intensity of the comparative example 16 that do not use stearic acid compound.

Suppose it is because the stearic acid compound of adding sticks to flowability and the lubrification of improving particulate mixtures in the metal pattern on the surface of particle, can form shaping density formed body in fact uniformly.

Even under the situation of the comparative example that does not use stearic acid compound, the anti-breakdown strength of formed body can improve by the graphite ratio that adds is increased to about 10%.Even so, consider the capacitance after the assemble in the end, poorer than embodiment 50～53.

For the five kinds of particulate mixtures that relatively are shaped become shaping density by compression molding is 3.20g/cm ³The hollow cylinder body time useful life of metal pattern, table 17 has been showed the change of using under the same conditions after about 1000 hours because of wear metal mould (material: SKD11, whole sclerosis HRC60) internal diameter.

As shown in Table 17, the change of metal pattern internal diameter is roughly relevant with creak, embodiment 50～53 is by adding stearic acid compound to stick to the lubrification of improving particulate mixtures on the particle surface, and stearic acid compound especially can be used for relaxing friction when removing (release) metal pattern from metal pattern.

As implied above, in these embodiment and comparative example, the present invention uses JIS standard LR type (size AA) battery, and the nickel-zinc primary battery of preparation same size.

Though battery is made on the anodal shaping mixt no problem ground of available embodiment, some comparative example can't form battery, because can break in its compression is packed into anodal box the time or broken.

Though adhere to the method for stearic acid compound on the surface of the granular mixture of priority of use granulation of the present invention, the present invention also can use when do stirring positive active material and graphite powder and add other method that stearic acid compound mixes stirring.

Yet the latter is than the former more difficult realization effect, because the concentration of stearic acid compound is lower on particle surface, the former is more excellent.

(embodiment 54 and comparative example 17)

By adding clorox and the accelerating oxidation effect, to obtain oxynickel hydroxide to 100 mass parts nickel hydroxide particles.

So the product that obtains is identified through XRD and is turned out to be compound oxynickel hydroxide particle, and confirms that by the residual titration of iron ammonium sulfate/potassinm permanganate nearly all Ni amount all becomes trivalent.

0.5 mass parts Y ₂O ₃Add 100 mass parts oxynickel hydroxides, as positive active material.

By adding carbon and electrolyte to this positive active material and being shaped the preparation anode mixture.

Consider the fabrication strength of anode mixture etc., with following mass ratio mixing and each component of shaping anode mixture.

Oxynickel hydroxide: carbon: electrolyte=100: 6: 5

In the case, shaping density is 3.22g/cm ³

About negative pole, cathode agent is by the no mercury and no hard lead preparation of the negative pole of use known manganese dioxide-zinc primary cell.The gel of zinc composition of cathode agent is as follows.

Zinc: absorbent binder: 12N KOH=100: 1.5: 55

At this moment, gel of zinc density is 2.70g/cm ³

About electrolyte, use the aqueous solution that mixes 12N KOH and 1N LiOH.

With anodal theoretical capacity is that 240mAh, negative pole theoretical capacity are 2640mAh (negative pole/positive electrode capacity is than=1.1), electrolyte ratio with respect to anodal theoretical capacity is the mode of 1.2ml/Ah, gel-filled in anodal jar of size AA counter-rotative type shown in Figure 1 anode mixture that obtains by said method and negative pole, assemble 18 batteries.

These batteries are divided into six groups, respectively comprise three batteries, and each Battery pack is put into the thermostat that remains on 10,20,30,40,60 and 80 ℃ respectively, and results of regular determination OCV measures with assessment OCV along with the variation that stores fate under normal temperature.It the results are shown in Fig. 3.

As shown in Figure 3, the effect susceptible of proof that high-temperature aging is adjusted OCV, (θ: t)=(40-80: 24-27) in the scope, wherein θ is a temperature, and t is the time.Though OCV adjust also can be in 100 ℃ thermostat timeliness because this is the temperature of boiling water, see unactual from the viewpoint of operating equipment.

As above describe in detail, the present invention uses high-temperature aging, have high OCV (open electric circuit voltage) battery self-discharge with can with other battery compatibility.This is that the self-discharge between the storage life is adjusted insufficient for OCV because battery is made approximately than it usually to be transported one month evening.Therefore, battery is forced at high temperature implement self-discharge.

Therefore, make than it under business condition that transport half a year in evening approximately at battery, OCV can reduce to proper range by self-discharge naturally, thereby need not be forced to implement self-discharge.

Use the self-discharge phenomenon of battery in this case, have with other that the battery of different OCV is compatible not to break away from design scope of the present invention.

(embodiment 55)

The used positive active material of this embodiment prepares in following mode.

At first, prepare the nickel hydroxide particle that 100 mass parts are doped with zinc and cobalt, and add 7 mass parts cobalt hydroxide particles., atmospheric environment in stir, spray 11 mass parts sodium hydrate aqueous solutions simultaneously,, obtain on nickel hydroxide surface, to have the compound nickel hydroxide of cobalt high order oxide skin(coating) subsequently by microwave heating thereafter.

Then, by adding oxidant such as clorox etc. with accelerating oxidation, can obtain the compound oxynickel hydroxide that covers by the high suboxide of cobalt to this system.

Products therefrom identifies that by XRD susceptible of proof is compound nickel hydroxide particle.

In addition, the ratio of trivalent is by the residual titration assessment of iron ammonium sulfate/potassinm permanganate, as oxygenation efficiency among the whole Ni.

This moment, the oxygenation efficiency of gained was 100%, and all nickle atoms are all trivalent.

Use this positive active material, under the fixedly atmosphere of relative humidity 80%, control temperature to 10,30,50 and 60 ℃, store any fate after, with its taking-up and carry out the mensuration of identical oxygenation efficiency.

It the results are shown in Fig. 4.

From Fig. 4 susceptible of proof oxygenation efficiency along with the time change to produce difference, if during the control temperature, even also be like this in up to 80% atmosphere having relative humidity.

That is, verified, be not higher than 30 ℃ of reduction deteriorations that can effectively prevent the high suboxide of nickel by keeping temperature.

Though non-certain, infer that its reason for by to the high suboxide control of nickel temperature, limits the amount of its saturated steam under this atmosphere, in other words, control absolute humidity can limit the kinetic energy of hydrone.

Self-discharge when storing about positive electrode, when considering positive active material particle ambient water molecule number and collision degree thereof, reduce the collision of hydrone by reducing temperature to positive active material, reduce the amount of the saturated steam under this atmosphere, promptly, by reducing the kinetic energy of hydrone number and minimizing hydrone, can effectively prevent the deterioration of the high suboxide of nickel.

In the present invention, storing experiment is to implement in 30 days by supposition time till assemble after the positive active material manufacturing.Yet the present invention needn't be limited.

In addition, active material is not limited to compound oxynickel hydroxide.

About manufacture method also is same.That is, use the oxynickel hydroxide that obtains by any oxidant of use also can get same effect.

By adding carbon and electrolyte to the positive active material that obtains by said method and be shaped, the preparation anode mixture.Fabrication strengths through considering anode mixture etc., each component of anode mixture is by following mass ratio combination.

Compound oxynickel hydroxide: carbon: 12N KOH=100: 6: 5

This moment, the density of gained formed body was about 3.22g/cm ³

About negative pole, use the no mercury of the negative pole of known manganese dioxide-zinc primary cell to prepare cathode agent with no hard lead.

The gel of zinc of cathode agent composed as follows.

Zinc: absorbent binder: 12N KOH=100: 1.5: 55

This moment, gel of zinc density was 2.70g/cm ³

About electrolyte, use the KOH aqueous solution of 12N.

The so anode mixture and the negative pole gel determination quality of gained, be packed in the jar, be that the mode of 1.3ml/Ah is injected electrolyte with ratio to the theoretical capacity of positive pole.Then, with the airtight metallic plate/negative pole top of incorporate airtight member, obtain AA size nickel-zinc primary battery shown in Figure 1 with collector body/gas release hole.

After being exposed under 20 ℃ the atmosphere three days at the battery of finishing and making it activation, in 20 ℃ atmosphere, implement the constant-current discharge that 150mA 1.0V blocks, measure discharge capacity.

As a result, confirm the oxygenation efficiency of gained positive active material herein and use between the discharge capacity of en closed nickel-zinc primary battery of its assembling and have linear relationship.

That is, confirm when filling the active material of same amount that keep the high oxidation rate person that high discharge capacity is provided, the person provides the low discharge amount to change over the low oxidation ratio.

Though relation does not elaborate about humidity and between between the storage life herein, the self-discharge of notice positive active material can further suppress by controlled humidity except temperature.

(embodiment 56)

Use the device of Fig. 5, at first preparation contains the spherical nickel hydroxide of eutectic of 5% zinc and 1% cobalt.

Reaction vessel 21 is provided with pipe 22, is used for separating nucleus and produces part and crystalline growth part.When 2M nickel sulfate solution, 0.158M zinc sulfate solution and 0.035M cobalt sulfate solution are supplied 25% aqueous ammonium of 8 volume % with constant ratio, 23 control pH arrive about 11.5～11.9 with the pH controller, the sodium hydroxide solution of while 6.5M without interruption, after one day time of staying stabilisation, slurries extract by the overflow technology.

In this operation, temperature remains on 37 ℃.

The gained slurries are repeated dehydration and washing, and when the pH of washings became 7～8, dehydration was also dry, finishes.

So the particle that obtains turns out to be the eutectic nickel hydroxide of 5% zinc and 1% cobalt, confirm that by the powder X-ray ray analysis crystal is nickel hydroxide (confirming that herein zinc and cobalt peak do not occur), by this powder of dissolving in hydrochloric acid and by the quantitative assay of atom light absorption method, confirm that 5% zinc and 1% cobalt are the eutectic form in nickel hydroxide.

Subsequently, contain 5% zinc that is the eutectic form and the nickel hydroxide particle of 1% cobalt adds 7 mass parts Co (OH) to 100 mass parts ₂, stir and spray 1 mass parts 10N NaOH, use microwave heating simultaneously, so that the compound nickel hydroxide particle of the high suboxide of cobalt to be arranged in its surface, further clorox is added this system with accelerating oxidation.At last, washing is also dry, obtains to comprise the compound oxynickel hydroxide of the high suboxide of cobalt.

So the product that obtains is identified through XRD and is turned out to be compound oxynickel hydroxide particle, and the residual titration by iron ammonium sulfate/potassinm permanganate confirms that nearly all Ni amount all becomes trivalent.

In addition, the Ni purity of compound oxynickel hydroxide is measured by EDTA titration or icp analysis at this moment, is evaluated as 54%.

Particle size distribution by laser technology also susceptible of proof compound oxynickel hydroxide this moment is D ₅₀Value is 10 μ m, the curve that distributes near rule in 1～20 μ m.

In addition, by using scanning electron microscopy to confirm that particle is spherical with accurate spherical aggregate.

Graphite and electrolyte are added in the positive active material that is obtained by said method, are 0.49 * 10 by using roller to roll device (WP230x80, Turbo Kogyo makes) at linear pressure ⁴～4.48 * 10 ⁴Roll processing under the N/cm, and use pelletizer (GRN-T-54S, Japanese Granulator makes) to carry out suitable granulation processing, preparation anode mixture particle.

In this operation, grain size grading is that the productive rate first time of 200～800 μ m is showed in table 18.

Usually, be recovered to roller when too thin and roll device constituting the powder granulation, be recovered to when too thick in the system of setting up departments of pelletizer and carry out granulation.Yet, when the first time, productive rate was high, can reduce active material because of the infringement of compression with friction.Therefore, this is epochmaking technology.

As shown in Table 18, the roller shaping stress that rolls device preferably is not less than 1.5 * 10 ⁴N/cm.

In this experiment, the limit of shaping stress is 4.48 * 10 ⁴N/cm is surpassing under its pressure, changes the preparation that makes compressing powder apart from the limiter effect and loses efficacy.

Consider that roller rolls the durability of device, 1.5 * 10 ⁴N/cm～3.5 * 10 ⁴The scope of N/cm is suitable.

Then, the forming pressure 1.51 * 10 that rolls device from roller ⁴N/cm～3.48 * 10 ⁴200～800 μ m granulated powder that N/cm obtains (by rolling) are filled in the size AA metal pattern, use any pressure forming, obtain the anode mixture particle with various shaping density.

Fabrication strengths through considering anode mixture etc., each component of anode mixture is mixed by following mass ratio.

Compound oxynickel hydroxide: carbon: 12N KOH=100: 6: 5

About negative pole, cathode agent is by the no mercury of the negative pole of use known manganese dioxide-zinc primary cell, unleaded kirsite preparation.

The gel of zinc of cathode agent composed as follows.

Zinc: absorbent binder: 12N KOH=100: 1.5: 55

This moment, gel of zinc density was 2.70g/cm ³

As electrolyte, use ZnO in 12N KOH solution is dissolved into saturated solution.

Use the various anode mixtures of gained like this, make anodal as the capacity regulating utmost point, measure its many negative pole gel of Capacity Ratio of certain mass, receive and keep in the jar, with the airtight metallic plate/negative pole top of incorporate airtight member, obtain size AA nickel-zinc primary battery shown in Figure 1 with collector body/gas release hole.

Discharge capacity and anodal utilance when 20 ℃ of following 100mA/0.8Vcut discharge, the shaping density with respect to anode mixture at this moment is showed in table 19.

As shown in Table 19, preferred anodal shaping density is 2.7～3.5g/cm ³

(comparative example 18)

The battery for preparing comparative example 18 by following method.

Except the used positive active material of embodiment, the battery of comparative example has same configuration basically.

Positive active material used herein with the nickel hydroxide particle that obtains by simple mixing sodium hydroxide solution and nickel sulfate solution as the basis.

This is the method for using traditionally for preparing nickel hydroxide.

That is, the method does not comprise the strict pH control of using aqueous ammonium, does not carry out constant agitation when chemical reaction.

In addition, the inner eutectic that does not also carry out zinc or cobalt.

In addition, its surface also covers without cobalt compound.

So the hydroxide nickel block of gained once imports in the known disintegrating machine, is broken into particle size distribution and approximately is same as typical alkaline manganese primary cell (MnO ₂-Zn primary cell) particle of used electrolytic manganese dioxide particle.

That is, be determined as D with laser technology ₅₀Value is 40～50 μ m, and the granularity that distributes in about 1～120 μ m.

In addition, with embodiment in the same manner, by become the oxynickel hydroxide particle with hypochlorite oxidation.

With its washing and dry, last, add slight stress to adjust particle diameter to the distribution that approximates greatly before the oxidation.

These particles are similarly identified through XRD and are turned out to be the oxynickel hydroxide particle, and confirm that by the residual titration of iron ammonium sulfate/potassinm permanganate nearly all Ni amount all becomes trivalent.

In addition, this moment, the Ni purity of oxynickel hydroxide was passed through the EDTA titration determination, was evaluated as 60%.

In addition, confirm that by scanning electron microscopy particle is unsetting.

Use the anode mixture that so obtains, the anode mixture of preparation and embodiment same composition is with shaping stress 0.51 * 10 ⁴～3.49 * 10 ⁴N/cm rolls processing (WP230 * 80, Turbo Kogyo makes), and carries out suitable granulation processing (GRN-T-54S, Japanese Granulator makes), obtains the granulation anode mixture.

In this operation, grain size grading is that the productive rate first time of 200～800 μ m is showed in table 20.

By the table 20 of comparative example 18 as can be known, the shaping range of stress that has high granulation productive rate in this system is 1.5 * 10 ⁴N/cm～2.5 * 10 ⁴N/cm; Even so, the situation in the table 18 of this productivity ratio embodiment 56 is all low.Therefore, verified embodiment is more excellent.

Especially, with embodiment in shaping stress in preferable range 1.5 * 10 ⁴N/cm～3.5 * 10 ⁴Productivity ratio under the N/cm than the time, the verified height of the productive rate of embodiment about 20%.

Infer that its reason is, because the oxynickel hydroxide particle is spherical, accurate spherical or its combination, thus when rolling, can relax stress concentrations, and this can promote the even compression and the fine and closely woven filling of particle, thereby can guarantee suitable intensity to the back granulation of pelletizer.

In this experiment, the limit of shaping stress is 3.49 * 10 ⁴N/cm is surpassing under its pressure, changes the preparation that makes compressing powder apart from the limiter effect and loses efficacy.

Infer that its reason is, existing oxynickel hydroxide particle is irregular, stress takes place when rolling concentrate.

Thereafter, by preferred forming pressure (passing through pelletizer) 1.52 * 10 in the comparative example ⁴N/cm～2.52 * 10 ⁴The granulated powder of 200～800 μ m that N/cm (by rolling) obtains is filled in the size AA metal pattern, uses any pressure forming, obtains having the anode mixture formed body of various shaping density.

Then, use these anode mixture formed bodies and the combination gel of zinc identical, the identical electrolyte that contains saturated ZnO etc., prepare the size AA nickel-zinc primary battery of same configuration with embodiment 56.

Discharge capacity and anodal utilance when 20 ℃ of following 100mA/0.8Vcut discharge, the shaping density of the anode mixture of this moment is showed in table 21 relatively.

By the table 21 of comparative example as can be known, the shaping density that obtains high discharge capacity in this system is 2.32～2.89g/cm ³Even so, any situation (2.45g/cm in the table 19 of this granulation productivity ratio embodiment ³Shaping density except) all low.Therefore, verified embodiment is more excellent.

Especially with embodiment in shaping density be 2.7～3.5g/cm in preferable range ³Under productivity ratio than the time, the verified height of the productive rate of embodiment about 20～250%.

When inferring spherical for using, accurate spherical or its combination of its reason as the oxynickel hydroxide particle, the density that not only is shaped but also utilance difference are big.

Supposition by the reason that the oxynickel hydroxide particle that uses embodiment 56 obtains high usage is, relaxes when rolling infringement to active material, because particle is spherically to compress filling easily, and contact is fully reliable between particle.

Its another reason is that the zinc and the cobalt of eutectic form contained in oxynickel hydroxide inside, and be stable in the configuration aspects of crystallography.

In addition, preparation is used among the embodiment 56 and obtains that the shaping density of high anodal utilance is 3.25g/cm ³The battery that anodal formed body is made, and be used in and obtain in the comparative example 18 that the shaping density of high anodal utilance is 2.52g/cm ³The battery made of anodal formed body, be exposed to 60 ℃ following 20 days of atmosphere.Then,, calculate its anodal utilance, and its initial under the same conditions anodal utilance (that is, is utilized 3.25g/cm in the table 19 by implementing down the 100mA/0.8Vcut discharge at 20 ℃ ³Anodal formed body battery anodal utilance 91%, use the 2.51g/cm in the table 21 ³The anodal utilance 65% of battery of anodal formed body) be decided to be 100%, assess relative utilance, as the capacity sustainment rate.In table 22, show.

Confirm that from table 22 from capacity sustainment rate viewpoint, embodiment 56 is better than comparative example 18.

Its reason is, because the oxynickel hydroxide particle of embodiment comprises zinc and cobalt is the eutectic form, suppresses self-discharge so its oxygen overvoltage is big.

Another reason is since in the oxynickel hydroxide particle pre-proeutectic zinc, when it stores, can receive and keep saturated zinc ion in electrolyte easily, the result can prevent that zinc dissolves in the electrolyte when negative pole stores, thereby can prevent the self-discharge that negative pole is interior.

Also infer, because positive pole prevents self-discharge respectively with negative pole, thus also suppress the generation that each extremely goes up oxygen and hydrogen, and then prevent of the redox of its antipole because of these gases, thus the better effect that prevents self-discharge caused.

Though embodiment shown here is essentially the AA size, it is not limited thereto, and can be applicable to various sizes.

In addition, though present embodiment has been showed the compound oxynickel hydroxide that uses at positive active material surface coverage high order cobalt compound, even confirm to use oxynickel hydroxide also can obtain same effect, positive active material is not restricted to this.

Industrial applicability

As mentioned above, en closed nickel-zinc primary battery of the present invention has the excellent specific property of capacity sustainment rate, energy density, high efficiency flash-over characteristic etc. when storing, and has high power capacity and can not damage the discharge rate characteristic.Therefore, the most suitable power supply of doing in various portable electronic devices such as portable receiver or the cassette recorder etc. especially is fit to the device that needs have the heavy duty characteristic.

Manufacture method according to en closed nickel-zinc primary battery of the present invention is marked down, easily, stably produce in large quantities according to heavy-duty battery of the present invention.

Table 1

Embodiment number	Anodal theoretical capacity (mAh)	Negative pole theoretical capacity (mAh)	The ratio of positive pole/negative pole theoretical capacity	The ratio of electrolyte (ml/Ah)	Anodal utilization rate (%)
						Embodiment 1	2510	2510	1.0	1.3	87
Embodiment 2	2290	2970	1.3	1.3	86
						Embodiment 3	2100	3350	1.6	1.3	86
Embodiment 4	2100	3350	1.6	1.6	90
						Embodiment 5	2100	3350	1.6	1.0	80
Comparative example 1	1890	3780	2.0	1.6	90
						Comparative example 2	1510	4530	3.0	1.6	89
Comparative example 3	2100	3350	1.6	0.8	42
						Comparative example 4	2100	3350	1.6	1.7	90

Table 2

Embodiment number	The ratio of negative pole/anodal theoretical capacity	Electrolyte ratio (ml/Ah)	Electrolyte is formed	Conductance (S/cm)	Anodal utilization rate (%)	Capacity sustainment rate (%)
							Embodiment 4	1.6	1.6	12N KOH	0.41	90	85
Embodiment 5	1.6	1.6	12N NaOH	0.20	72	95
							Embodiment 6	1.6	1.6	12N KOH +1N LiOH	0.35	85	93
Comparative example 5	1.6	1.6	12N NaOH +1N LiOH	0.16	30	98
							Comparative example 8	1.6	1.6	12N KOH +1N NaOH	0.40	90	91

Table 3

Embodiment number	The ratio of negative pole/anodal theoretical capacity	Electrolyte ratio (ml/Ah)	Electrolyte is formed	Anode additive (quality %)	Anodal utilance (%)	Capacity sustainment rate (%)
							Embodiment 9	1.6	1.6	12N KOH	Y 2O 3	89	92
Embodiment 10	1.6	1.6	12N KOH	Er 2O 3	89	90
							Embodiment 11	1.6	1.6	12N KOH	Yb 2O 3	89	90
Embodiment 12	1.6	1.6	12N KOH	CaF 2	90	91
							Embodiment 13	1.6	1.6	12N KOH +1N NaOH	Yb 2O 3	90	95

Table 4

	Anodal quality (g)	Non-solid part accounts for the volume ratio of positive active material	The volume occupation rate of non-solid part (volume %)	Theoretical discharge capacity (mAh)	150mA discharge capacity (mAh)	1000mA discharge capacity (mAh)	150mA utilance (%)	1000mA utilance (%)
									Ratio example 6	8.7	0.52	32％	1910	1413	573	74	30
Embodiment 14	9.0	0.46	29％	1980	1743	852	88	43
									Embodiment 15	9.3	0.41	27％	2051	1825	1046	89	51
Embodiment 16	9.6	0.36	24％	2121	1909	1209	90	57
									Embodiment 17	10.0	0.31	22％	2192	1994	1359	91	62
Embodiment 18	10.3	0.26	19％	2262	2036	1335	90	59
									Embodiment 19	10.6	0.22	17％	2332	2099	1283	90	55
Comparative example 7	10.9	0.18	14％	2403	1970	649	82	27

Table 5

	The mixing ratio of positive active material (quality %)	The mixing ratio of graphite (quality %)	The mixing ratio of electrolyte (quality %)	Non-solid part accounts for the volume ratio of positive active material	The volume occupation rate of non-solid part	Theoretical discharge capacity (mAh)	150mA discharge capacity (mAh)	1000 mA discharge capacities (mAh)	150mA utilance (%)	1000mA utilance (%)
											Embodiment 20	98％	0.0％	2.3％	0.30	23％	2379	2117	1309	89	55
Embodiment 21	94％	2.7％	3.5％	0.31	23％	2285	2057	1348	90	59
											Embodiment 17	90％	5.4％	4.6％	0.31	22％	2192	1994	1359	91	62
Embodiment 22	86％	8.1％	5.8％	0.31	21％	2098	1888	1259	90	60
											Comparative example 8	82％	10.8％	6.9％	0.31	20％	2004	1704	1022	85	51

Table 6

	Cladding material	The volume occupation rate of non-solid part (volume %)	Theoretical discharge capacity (mAh)	150mA discharge capacity (mAh)	1000mA discharge capacity (mAh)	150mA utilance (%)	1000mA utilance (%)
								Embodiment 17	Cobalt hydroxide	22％	2192	1994	1359	91	62
Embodiment 23	Metal Ni	22％	2192	1972	1315	90	60
								Embodiment 24	Metal Co	22％	2192	1929	1271	88	58
Comparative example 9	Do not have and cover	22％	2192	1819	1140	83	52

Table 7

Sample	The endothermic temperature peak (℃)	Resistivity (Ω cm)	Having or not of γ oxynickel hydroxide
				Embodiment 25	235	10	Comprise
Embodiment 26	235	3	Comprise
				Embodiment 27	235	30	Comprise
Embodiment 28	235	50	Comprise
				Embodiment 29	235	100	Comprise
Embodiment 30	235	10	Do not comprise
				Embodiment 31	200	90	Comprise
Embodiment 32	260	30	Comprise
				Comparative example 10	280	30	Comprise
Comparative example 11	180	15	Comprise

Table 8

Sample	Theoretical discharge capacity	The 150mA discharge capacity	The 1000mA discharge capacity	The 150mA utilance	The 1000mA utilance
						Embodiment 25	2200	1995	1380	91	63
Embodiment 26	2150	1962	1377	93	65
						Embodiment 27	2105	1966	1288	91	60
Embodiment 28	2150	1933	1201	90	55
						Embodiment 29	2150	1921	1103	89	51
Embodiment 30	2220	1998	1403	90	63
						Embodiment 31	2150	1935	1118	90	52
Embodiment 32	2100	1911	1260	91	60
						Comparative example 10	2150	508	210	23	4
Comparative example 11	2150	1570	855	73	40

Table 9

Sample	Specific area (the m of carbon granule 2/g)	The content of carbon granule (quality %)
			Comparative example 12	0.9	8.1
Embodiment 33	3.4	8.1
			Embodiment 34	1.7	8.1
Embodiment 35	14	8.1
			Embodiment 36	30	8.1
Embodiment 37	80	8.1
			Embodiment 38	145	8.1
Embodiment 39	270	8.1
			Comparative example 13	320	8.1

Table 10

Sample	Theoretical discharge capacity (mAh)	150mA discharge capacity (mAh)	1000mA discharge capacity (mAh)	150mA utilance (%)	1000mA utilance (%)
						Comparative example 12	2126	1811	451	85.2	21.2
Embodiment 33	2126	1856	882	87.3	41.5
						Embodiment 34	2126	1911	1118	89.9	52.6
Embodiment 35	2126	1960	1284	92.2	60.4
						Embodiment 36	2126	1981	1341	93.2	63.1
Embodiment 37	2126	1945	1329	91.5	62.5
						Embodiment 38	2126	1873	1269	88.1	59.7
Embodiment 39	2126	1684	1184	79.2	55.7
						Comparative example 13	2126	1563	1063	73.5	50.2

Table 11

Sample	Specific area (the m of carbon granule 2/g)	The content of carbon granule (quality %)
			Comparative example 14	30	2.7
Embodiment 40	30	5.4
			Embodiment 36	30	8.1
Embodiment 41	30	10.8
			Embodiment 42	30	13.5
Comparative example 15	30	16.2

Table 12

Sample	Theoretical discharge capacity (mAh)	150mA discharge capacity (mAh)	1000mA discharge capacity (mAh)	150mA utilance (%)	1000mA utilance (%)
						Comparative example 14	2257	1607	479	71.2	21.2
Embodiment 40	2192	1913	1116	87.3	50.9
						Embodiment 36	2126	1981	1341	93.2	63.1
Embodiment 41	2060	1920	1218	93.2	59.1
						Embodiment 42	1994	1861	1067	93.3	53.5
Comparative example 15	1929	1759	753	91.2	39.3

Table 13

Sample	Specific area is 14m 2The mixing ratio of the graphite granule of/g (quality %)	Specific area is 270m 2The mixing ratio of the graphite granule of/g (quality %)	The content of graphite granule (quality %)
				Embodiment 35	100	0	8.1
Embodiment 43	80	20	8.1
				Embodiment 44	70	30	8.1
Embodiment 45	60	40	8.1
				Embodiment 46	50	50	8.1
Embodiment 47	40	60	8.1
				Embodiment 48	30	70	8.1
Embodiment 49	20	80	8.1
				Embodiment 39	100	0	8.1

Table 14

Sample	Theoretical discharge capacity (mAh)	150mA discharge capacity (mAh)	1000mA discharge capacity (mAh)	150mA utilance (%)	1000mA utilance (%)
						Embodiment 35	2126	1960	1284	92.2	60.4
Embodiment 43	2126	1977	1329	93.0	62.5
						Embodiment 44	2126	2011	1367	94.6	64.3
Embodiment 45	2126	2037	1426	95.8	67.1
						Embodiment 46	2126	2049	1475	96.4	69.4
Embodiment 47	2126	2026	1465	95.3	68.9
						Embodiment 48	2126	1983	1416	93.3	66.6
Embodiment 49	2126	1892	1341	89.0	63.2
						Embodiment 39	2126	1684	1184	79.2	55.7

Table 15

Embodiment and comparative example number	Creak
		Embodiment 50	No creak
Embodiment 51	No creak
		Embodiment 52	No creak
Embodiment 53	No creak
		Comparative example 16	Quite big creak

Table 16

Embodiment and comparative example number	Crushing strength (N)
		Embodiment 50	7.49
Embodiment 51	7.45
		Embodiment 52	7.43
Embodiment 53	7.40
		Comparative example 16	4.88

Table 17

Embodiment and comparative example number	The internal diameter size rate of change
		Embodiment 50	0.197％
Embodiment 51	0.202％
		Embodiment 52	0.206％
Embodiment 53	0.201％
		Comparative example 16	0.409％

Table 18

Shaping stress (* 10 4N/cm)	Granulation productive rate (%) for the first time
		0.49	45
0.99	50
		1.51	55
2.02	58
		2.51	61
2.99	63
		3.48	64
3.97	64
		4.48	64

Table 19

Shaping density (g/cm 3)	Discharge capacity (mAh)	Anodal utilance (%)
			2.45	1349	80
2.72	1647	88
			3.04	1925	92
3.25	2058	92
			3.52	2180	90
3.82	2077	79

Table 20

Shaping stress (* 10 4N/cm)	Granulation productive rate (%) for the first time
		0.51	27
1.02	33
		1.52	37
2.01	41
		2.52	44
3.03	44
		3.49	44

Table 21

Shaping density (g/cm 3)	Discharge capacity (mAh)	Anodal utilance (%)
			2.11	886	61
2.32	1134	71
			2.51	1278	74
2.89	1392	70

Table 22

Battery types	Capacity sustainment rate (%)
		Embodiment 56	70
Comparative example 18	58

Claims (35)

1. en closed nickel-zinc primary battery, possess with the anode mixture of nickel series compounds particle as positive active material, it is characterized in that: anodal theoretical capacity is 1.0～1.6 with the ratio of negative pole theoretical capacity, and the ratio of alkaline electrolyte and above-mentioned anodal theoretical capacity is 1.0～1.6ml/Ah.

2. en closed nickel-zinc primary battery as claimed in claim 1, it is characterized in that: receiving and keeping in metal can has: disperse the gelled negative electrode and the dividing plate that form as the alloy powder of key component with zinc by the anodal formed body that forms as the anode mixture compression molding of positive active material with above-mentioned nickel series compounds particle, in alkaline electrolyte, the non-solid part of above-mentioned anodal formed body and the volume ratio of above-mentioned positive active material are 0.2: 1～0.5: 1, are 15～30 volume % and above-mentioned non-solid part accounts for the volume occupation rate of above-mentioned anodal formed body.

3. en closed nickel-zinc primary battery as claimed in claim 1 or 2 is characterized in that: above-mentioned en closed nickel-zinc primary battery has inversion structures.

4. en closed nickel-zinc primary battery as claimed in claim 1 or 2 is characterized in that: above-mentioned positive active material is an oxynickel hydroxide based compound particle.

5. en closed nickel-zinc primary battery as claimed in claim 4 is characterized in that: above-mentioned oxynickel hydroxide based compound particle contains the γ oxynickel hydroxide.

6. en closed nickel-zinc primary battery as claimed in claim 4 is characterized in that: above-mentioned oxynickel hydroxide based compound particle is that oxynickel hydroxide particle or eutectic have independent zinc and cobalt or the oxynickel hydroxide particle of the two.

7. en closed nickel-zinc primary battery as claimed in claim 4 is characterized in that: above-mentioned positive active material further comprises the compound that is selected from least a metal in the group that yttrium, ytterbium, erbium and calcium forms.

8. en closed nickel-zinc primary battery as claimed in claim 4 is characterized in that: above-mentioned positive active material is had independent zinc and cobalt or the oxynickel hydroxide particle of the two for the surface by oxynickel hydroxide particle or the eutectic that the high suboxide of cobalt, metallic cobalt or metallic nickel cover.

9. en closed nickel-zinc primary battery as claimed in claim 8, the high suboxide of cobalt that wherein covers above-mentioned positive active material are at least one material that is selected from the group that cobalt hydroxide, cobaltosic oxide, cobalt sesquioxide, cobalt black and cobalt hydroxide form.

10. en closed nickel-zinc primary battery as claimed in claim 8, it is characterized in that: above-mentioned positive active material is made of by the oxynickel hydroxide particle that the high suboxide of cobalt covers the surface, and above-mentioned particle has endothermic peak in 200～260 ℃ of scopes in differential thermal analysis.

11. en closed nickel-zinc primary battery as claimed in claim 10 is characterized in that: the resistivity that the above-mentioned positive active material that is capped is the nickel series compounds particle is not higher than 100 Ω cm.

12. en closed nickel-zinc primary battery as claimed in claim 1 or 2 is characterized in that: above-mentioned positive active material is the oxynickel hydroxide based compound particle of spherical, accurate spherical or the two aggregate.

13. en closed nickel-zinc primary battery as claimed in claim 1 is characterized in that: contain carbon granule in the above-mentioned anode mixture, the amount of this carbon granule accounts for 3～15 quality % of above-mentioned anode mixture.

14. en closed nickel-zinc primary battery as claimed in claim 13, wherein the amount of carbon granule accounts for its 3～10 quality % in described anode mixture.

15. en closed nickel-zinc primary battery as claimed in claim 13 is characterized in that: the specific area of above-mentioned carbon granule is 1.0～300m ²/ g.

16. en closed nickel-zinc primary battery as claimed in claim 15 is characterized in that: above-mentioned carbon granule is the mixture of the different carbon granule of at least two kinds of specific areas.

17. en closed nickel-zinc primary battery as claimed in claim 16 is characterized in that: above-mentioned carbon granule is that the specific area of 25～75 quality % is 1.0～30m ²The specific area of the carbon granule of/g and 75～25 quality % is 30～300m ²The mixture of the carbon granule of/g.

18. en closed nickel-zinc primary battery as claimed in claim 13 is wherein containing stearic acid compound in as the nickel series compounds particle of above-mentioned positive active material and the above-mentioned anode mixture of carbon granule as key component.

19. en closed nickel-zinc primary battery as claimed in claim 18 is characterized in that: above-mentioned stearic acid compound with the mixed of 0.05～0.5 quality % in above-mentioned anode mixture.

20. en closed nickel-zinc primary battery as claimed in claim 1 is characterized in that: above-mentioned alkaline electrolyte is selected from material in the group that potassium hydroxide, NaOH and lithium hydroxide form as its solute by at least a, and conductance is not less than 0.2S/cm.

21. en closed nickel-zinc primary battery as claimed in claim 1 or 2, it is characterized in that: be in battery case, to receive and keep to have: the anodal formed body of the hollow circle tube for preparing by the mixture compression molding of anode mixture, above-mentioned anode mixture with spherical, roughly spherical or the two the nickel series compounds particle of aggregate is as positive active material; Be disposed at the dividing plate in the hollow bulb of the anodal formed body of above-mentioned hollow circle tube; And the counter-rotative type battery that contains the gelled negative electrode of the alkaline electrolyte in the aforementioned barriers of packing into.

22. en closed nickel-zinc primary battery as claimed in claim 1, it is characterized in that: receiving and keeping in metal can has: by the anodal formed body that forms as the anode mixture compression molding of positive active material with the nickel series compounds particle, being distributed to gelled negative electrode and the dividing plate that forms in the alkaline electrolyte with zinc as the alloy powder of key component, above-mentioned anodal formed body contains lubricant.

23. en closed nickel-zinc primary battery as claimed in claim 22 is characterized in that: above-mentioned lubricant is an ethylenebisstearamide.

24. method of making en closed nickel-zinc primary battery, this en closed nickel-zinc primary battery, use the nickel series compounds particle as positive active material, anodal theoretical capacity is 1.0～1.6 with the ratio of negative pole theoretical capacity, and alkaline electrolyte is 1.0～1.6ml/Ah with the ratio of above-mentioned anodal theoretical capacity, the method is characterized in that:

With spherical, accurate spherical or the two the nickel series compounds particle of aggregate as positive active material, and mix carbon granule at least in above-mentioned positive active material and the anode mixture of preparation, it is granular that granulation becomes;

By compression molding it is configured as the anodal formed body of hollow circle tube;

The anodal formed body of above-mentioned hollow circle tube is received and kept in metal can;

Dividing plate is inserted the hollow cylinder inside of above-mentioned anodal formed body;

Be stored in that to be dispersed with in the alkaline electrolyte with zinc be the negative electrode gel that the alloy powder of main component forms;

Negative electrode collector is inserted in the gelled negative electrode;

With the airtight above-mentioned jar opening of jar coffer.

25. the manufacture method of en closed nickel-zinc primary battery as claimed in claim 24 is characterized in that:

With above-mentioned after to be nickel series compounds and carbon granule with positive active material as the mixture granulation of the anode mixture of key component become granular step, also have stearic acid compound is added step in the above-mentioned granular anode mixture.

26. the manufacture method as claim 24 or 25 described en closed nickel-zinc primary batteries is characterized in that: implement high-temperature aging in battery assembling back.

27. the manufacture method of en closed nickel-zinc primary battery as claimed in claim 26 is characterized in that: above-mentioned high-temperature aging is to carry out under 40～80 ℃ 24～72 hours in temperature.

28. the manufacture method of en closed nickel-zinc primary battery as claimed in claim 24 is characterized in that: the temperature that is stored in of the above-mentioned nickel series compounds before the battery assembling is carried out below 30 ℃.

29. a battery is with compressing the nickel series compounds positive pole, be used for en closed nickel-zinc primary battery, the anodal theoretical capacity of this en closed nickel-zinc primary battery is 1.0～1.6 with the ratio of negative pole theoretical capacity, and alkaline electrolyte is 1.0～1.6ml/Ah with the ratio of above-mentioned anodal theoretical capacity, this positive pole is the nickel positive pole that forms as the mixture compression molding of positive active material with the nickel series compounds particle, it is characterized in that: above-mentioned nickel series compounds particle is spherical, accurate spherical or the aggregate of the two, and is the oxynickel hydroxide particle.

30. battery as claimed in claim 29 is with compressing the nickel series compounds positive pole, it is characterized in that: the average particle size range of above-mentioned nickel series compounds particle is 1～50 μ m.

31. the battery manufacture method of compression nickel series compounds positive pole, this positive pole is used for en closed nickel-zinc primary battery, this en closed nickel-zinc primary battery uses the nickel series compounds particle as positive active material, anodal theoretical capacity is 1.0～1.6 with the ratio of negative pole theoretical capacity, and the ratio of alkaline electrolyte and above-mentioned anodal theoretical capacity is 1.0～1.6ml/Ah, above-mentioned manufacture method comprises:

Mix and the stirring inorganic nickel aqueous solution and alkaline aqueous solution, separate out the step of nickel hydroxide based compound particle;

Cover the step of above-mentioned nickel hydroxide based compound particle surface with cobalt compound;

Oxidation converts it into the step of the oxynickel hydroxide based compound particle that is covered by cobalt compound by the above-mentioned nickel hydroxide based compound particle that above-mentioned cobalt compound covers;

The anode mixture additive is added in the oxynickel hydroxide based compound particle that is covered by above-mentioned cobalt compound, and the step of the anode mixture mixture of granulation generation; And

With the compression molding of above-mentioned granulation anode mixture is the step of anodal formed body.

32. the battery as claimed in claim 31 manufacture method of compression nickel series compounds positive pole is characterized in that:

Above-mentioned with in the above-mentioned oxynickel hydroxide based compound particle of anode mixture additive adding by the cobalt compound covering, and the step of the anode mixture mixture of granulation generation, comprise at least:

The mixture of above-mentioned anode mixture is imported the procedure of processing that rolls for preparing compressing powder between two rollers;

Above-mentioned compressing powder is imported the granulation procedure of processing of between the two rollers that have chimeric protuberance on its roller surface, carrying out granulation; And

Use sieve that this granulated powder is classified into the classification procedure of processing of particle size range arbitrarily.

33. the battery as claimed in claim 32 manufacture method of compression nickel series compounds positive pole, it is characterized in that: prepare the rolling in the procedure of processing of compressing powder between above-mentioned pair of roller above-mentioned above-mentioned anode mixture mixture is imported, two roller per unit lengths apply 1.5 * 10 ⁴～3.5 * 10 ⁴The stress of N/cm is to the mixture of above-mentioned anode mixture.

34. according to the manufacture method with compression nickel series compounds positive pole of each described battery in the claim 31～33, it is characterized in that: above-mentioned use sieve becomes above-mentioned efflorescence powder classification that grading range is 200～800 μ m in the classification procedure of processing of particle size range arbitrarily.

35. battery as claimed in claim 34 with the manufacture method of compression nickel series compounds positive pole, is characterized in that: above-mentioned will the preparation in the step of anodal formed body through the anode mixture compression molding of granulation, classification, anodal shaping density is 2.7～3.5g/cm ³

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