CN1957490A - Alkaline battery - Google Patents
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- CN1957490A CN1957490A CNA2005800165198A CN200580016519A CN1957490A CN 1957490 A CN1957490 A CN 1957490A CN A2005800165198 A CNA2005800165198 A CN A2005800165198A CN 200580016519 A CN200580016519 A CN 200580016519A CN 1957490 A CN1957490 A CN 1957490A
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- nickel oxide
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Abstract
An alkaline battery comprising a positive electrode mix and a negative electrode and, interposed therebetween, a separator, the positive electrode mix containing nickel oxyhydroxide, manganese dioxide and a conduction aid, wherein (1) at least manganese is solid dissolved in the nickel oxyhydroxide, the manganese occupying 0.5 to 10 mol% of the sum of metal elements contained in the nickel oxyhydroxide, and wherein (2) the nickel oxyhydroxide is composed mainly of a ss-crystal structure, and wherein (3) the nickel oxyhydroxide has an average particle diameter on volume basis of 8 to 15 mum. By virtue of the use of the above positive electrode mix, a capacity increase and an enhancement of storage characteristics can be accomplished for the alkaline battery. Further, by causing the nickel oxyhydroxide having manganese solid dissolved therein to have the above properties, there can be accomplished a striking enhancement of the productivity of the nickel oxyhydroxide.
Description
Technical field
The present invention relates to a kind of possess contain hydroxy nickel oxide and manganese dioxide alkaline battery as the anode mixture of active material.
Background technology
With the alkaline manganese dry cell is the structure that the alkaline battery of representative has the outer carbon type (inside-out) of following interior zinc, promptly, among the anodal shell of double as positive terminal, to be configured to by the anode mixture particle (pellet) that manganese dioxide cylindraceous constitutes contact closely with anodal shell, and in the inboard of this particle across diaphragm configuration gelatinous zinc negative pole.Be accompanied by popularizing of in recent years digital device, use the bearing power of the equipment of these batteries to increase gradually.For this reason, wish to have the battery of strong load discharge function admirable.For example, in order to improve strong load discharge characteristic, proposed in anode mixture, to mix the scheme (with reference to patent documentation 1) of hydroxy nickel oxide.In recent years, such battery is actual uses and has obtained extensively popularizing.
Used hydroxy nickel oxide in the above-mentioned alkaline battery for example is to make (with reference to the patent documentation 2) that obtains of oxidant oxidations such as aqueous sodium hypochlorite solutions by can be used as the nickel hydroxide spherical or the egg shape that the alkaline battery purposes uses.At this moment, spherical nickel hydroxide as raw material, can use the material of the big β type of bulk density (perhaps being called " bulk density " or " tap density "), it is used oxidizer treatment, be converted into the crystal structure of β type spherical hydroxy nickel oxide as main body.By using this kind hydroxy nickel oxide, just can obtain highdensity positive pole.Consequently, can be with cell high-capacityization.
On the other hand, in anode mixture, mixed the alkaline battery of hydroxy nickel oxide and compared, had the problem of retention difference with the alkaline battery of hydroxyl nickel oxide not.When particularly at high temperature preserving, have anodal self discharge sometimes and become big situation.This self discharge reaction is made of the reduction reaction of the hydroxy nickel oxide shown in the formula (1) and the oxidative decomposition of the hydroxide ion shown in the formula (2), as a whole, becomes reaction as the formula (3).
So, in the battery after preservation,, need the self discharge reaction shown in the inhibition formula (3) in order to keep strong load discharge characteristic, avoid the deterioration of hydroxy nickel oxide.
For example, in order to suppress this self discharge reaction, proposed to use the scheme (with reference to patent documentation 3) of the solid solution hydroxy nickel oxide that contains a spot of zinc.Contain in the solid solution hydroxy nickel oxide of zinc at this kind, the overvoltage that its lip-deep oxygen produces raises, and can suppress the reaction of above-mentioned formula (2).Thus, even mixed the alkaline battery of hydroxy nickel oxide in the anode mixture, also retention can be brought up to certain degree.
As similar techniques, the scheme (with reference to patent documentation 4) of the hydroxy nickel oxide that contains a little zinc and cobalt and the scheme (with reference to patent documentation 5) of using the hydroxy nickel oxide that contains a small amount of alkaline-earth metal (for example calcium) have been proposed to use.
In addition, in order to reduce the self discharge of battery, following scheme (with reference to patent documentation 6) was proposed also, promptly, after having prepared hydroxy nickel oxide, this hydroxy nickel oxide be impregnated in the alkaline aqueous solution, forcibly make alkaline kation contain interlayer at the hydroxy nickel oxide crystal.
Patent documentation 1: the spy opens clear 57-72266 communique
Patent documentation 2: special fair 4-80513 communique
Patent documentation 3: the spy opens the 2002-75354 communique
Patent documentation 4: the spy opens the 2002-203546 communique
Patent documentation 5: the spy opens the 2002-289187 communique
Patent documentation 6: the spy opens the 2001-325954 communique
But, under the situation of the solid solution hydroxy nickel oxide that uses the aforesaid metallic element that contains a little zinc, cobalt, alkaline-earth metal and so on, have following problem.
1) contains the solid solution hydroxy nickel oxide of zinc
The solid solution hydroxy nickel oxide that contains zinc is to make of oxidizer treatment by the solid solution nickel hydroxide that will contain zinc.As in the field of alkaline battery known, the zinc of solid solution in nickel hydroxide has the effect of the oxidation that suppresses nickel.Thus, solid solution the nickel hydroxide of zinc be difficult to oxidized dose of oxidation, the nickel hydroxide of remained unreacted easily in hydroxy nickel oxide.Like this, for solid solution the nickel hydroxide oxidation fully of zinc, just need to add excessive greatly oxidant and implement long time treatment.Thus, just be difficult to the productivity ratio hydroxy nickel oxide of zinc of having made solid solution well.
2) contain the solid solution hydroxy nickel oxide of cobalt or contain cobalt and the solid solution hydroxy nickel oxide of zinc
Contain cobalt or contain cobalt and the solid solution hydroxy nickel oxide of zinc is by containing cobalt or containing cobalt and the solid solution nickel hydroxide of zinc is made of oxidizer treatment.Though cobalt reduces the oxidation-reduction potential of nickel and makes the oxidation of oxidant more easy, yet when the discharge of hydroxy nickel oxide, have the situation that its current potential is reduced.That is to say that the flash-over characteristic of the battery of made has the tendency of reduction.In addition, because the price comparison height of cobalt, so this kind hydroxy nickel oxide problem of also having cost to uprise.
3) contain the solid solution nickel hydroxide of alkaline-earth metal
The solid solution nickel hydroxide that contains alkaline-earth metal is to make of oxidizer treatment by the solid solution nickel hydroxide that will contain alkaline-earth metal.At first, to solid solution the nickel hydroxide of alkaline-earth metal when synthesizing because the sulfate of alkaline-earth metal is most water insoluble, therefore need use in water as the nitrate aqueous solution of the alkaline-earth metal of solubility etc.Thus, what just need nitrate anion removes operation etc., compares with general the synthetic of nickel hydroxide, and it is complicated that operating condition becomes.In addition, because the alkaline-earth metal of solid solution in nickel hydroxide also has the effect of the oxidation that suppresses nickel in the same manner with zinc, therefore be difficult to improve the productivity ratio of oxidation operation.
Summary of the invention
The present invention relates to a kind of alkaline battery, it possesses anode mixture, negative pole, is disposed at the barrier film between anode mixture and the negative pole.Here, anode mixture contains hydroxy nickel oxide, manganese dioxide and conductive agent, and wherein, (1) in this hydroxy nickel oxide, solid solution has manganese at least, and this manganese accounts for 0.5～10mol% of the total amount of metallic element contained in this hydroxy nickel oxide.In addition, (2) hydroxy nickel oxide with the crystal structure of β type as main body.And, (3) hydroxy nickel oxide be that the average grain diameter of benchmark is 8～15 μ m with the volume.
In described alkaline battery, hydroxy nickel oxide preferably further satisfies at least a in the following rerum natura:
(4) the average valence mumber of nickel is 2.95～3.05;
(5) bulk density is 2.15g/cm
3More than;
(6) the BET specific area is 5～20m
2/ g
Here, so-called " bulk density " is meant the bulk density of having carried out 300 hydroxy nickel oxides after the knocking.
In above-mentioned alkaline battery, hydroxy nickel oxide has preferably supported sodium ion on its surface, and sodium ion accounts for 0.5～1 weight % of the total amount of hydroxy nickel oxide and sodium ion.
In described alkaline battery, hydroxy nickel oxide preferably accounts for 10～80 weight % of anode mixture.
In described alkaline battery, conductive agent is preferably graphite, and graphite accounts for 3～10 weight % of anode mixture.
According to the present invention, can seek in anode mixture, to contain the high capacity of alkaline battery of hydroxy nickel oxide and manganese dioxide and the raising of preservation characteristics.
In addition and since solid solution the hydroxy nickel oxide of manganese have aforesaid physics value, thereby also can increase substantially the productivity ratio of this hydroxy nickel oxide.Like this, just can supply with strong load discharge characteristic or the good alkaline battery of reliability at an easy rate.
Description of drawings
Fig. 1 is the front view that a part of section with the alkaline battery of an embodiment of the invention forms.
Fig. 2 be expression among the embodiment used solid solution the figure of X-ray diffraction spectrogram separately of the nickel hydroxide of Mn (curve A) and nickel hydroxide (curve B) that Mn is contained with the eutectic state.
Embodiment
Among Fig. 1, represented the alkaline battery of one embodiment of the invention.
This alkaline battery possesses anode mixture 2, gelled negative electrode 3, is disposed at barrier film 4, electrolyte (not shown) between anode mixture 2 and the gelled negative electrode 3 and the anodal shell 1 of accommodating them.
Anodal shell 1 has formed round-ended cylinder shape, has outstanding laterally teat in bottom center.This teat plays a role as positive terminal.
In the inside of anodal shell 1, dispose the anode mixture 2 of hollow cylindrical in the mode that contacts with anodal shell 1.At the inner face of anodal shell 1, be formed with graphite applying film 10.
In the inboard of anode mixture 2, dispose gelled negative electrode 3 across barrier film 4.In addition, gelled negative electrode 3 and anodal shell 1 are insulated by insulator cap 9.
In gelled negative electrode 3, inserted negative electrode collector 6.Negative electrode collector 6 is chimeric with the medium pore of resin system hush panel 5.At the top of negative electrode collector 6, be welded with base plate 7.Base plate 7 double as negative terminals.
The peristome of anodal shell 1 is by carrying out the open end of anodal shell 1 ca(u)lk and sealed across the periphery of the periphery of hush panel 5 and base plate 7.The outer surface of anodal shell 1 covers with outer dress label 8.
Above-mentioned electrolyte is in order to make anode mixture 2 and barrier film 4 moistening and use.As this electrolyte, can use electrolyte known in this field.As an example, can list the aqueous solution of the potassium hydroxide that contains 40 weight %.
As above-mentioned gelled negative electrode 3, can use material known in this field.For example, as this kind gelled negative electrode, can list by as the Sodium Polyacrylate of gelating agent, alkaline electrolyte and as the zinc powder of negative electrode active material and the negative pole that constitutes.And alkaline electrolyte used in the gelled negative electrode both can be identical with above-mentioned electrolyte, also can be different.
The crystal structure of this hydroxy nickel oxide is based on the crystal structure of the high β type of density.At this moment, the crystal structure of β type preferably accounts for more than 90% of crystal structure of hydroxy nickel oxide.This be because: when the content of the crystal of β type was less than 90%, then the bulk density of hydroxy nickel oxide or bulk density reduced, thereby the density of the hydroxy nickel oxide of filling in the shell of specified volume reduces.
Hydroxy nickel oxide be that the average grain diameter of benchmark is 8～15 μ m with the volume.When the average grain diameter of hydroxy nickel oxide less than 8 μ m or average grain diameter during greater than 15 μ m, have then that anode mixture particle exposure level each other etc. reduces, the capacity when preserving reduces the situation that becomes big.
Therefore, have the average grain diameter of 8～15 μ m by making described hydroxy nickel oxide, then battery capacity will improve, and tails off self decomposing of hydroxy nickel oxide, can improve the retention of battery widely.
As mentioned above, one of principal character of the present invention is that solid solution has manganese at least in hydroxy nickel oxide.Present inventors further investigate various nickel hydroxides or hydroxy nickel oxide, found that, at least solid solution the nickel hydroxide of an amount of manganese be very easy to carry out chemical oxidation with oxidant.
In addition, because solid solution has manganese in hydroxy nickel oxide, therefore the conductivity of this hydroxy nickel oxide can be kept than the highland.Therefore, when manganese dioxide discharges after the discharge of hydroxy nickel oxide, also can from manganese dioxide, obtain enough capacity.
Above-mentioned hydroxy nickel oxide preferably has more than in the following rerum natura any one:
(4) the average valence mumber of nickel is 2.95～3.05;
(5) bulk density is 2.15g/cm
3More than;
(6) the BET specific area is 5～20m
2/ g
When in the above-mentioned hydroxy nickel oxide nickeliferous average valence mumber less than 2.95 the time, then, therefore have the situation that the capacity of battery reduces because the capacity of the per unit weight of hydroxy nickel oxide tails off.On the other hand, when the average valence mumber of this nickel surpassed 3.05, then in hydroxy nickel oxide, the ratio of γ type crystal increased, and has the situation that strong load discharge characteristic reduces.Here, in the hydroxy nickel oxide nickeliferous flat fare numerical example try to achieve as using ICP luminesceence analysis shown below and redox titration method.
(A) mensuration of the weight metal ratio in the hydroxy nickel oxide
The hydroxy nickel oxide of ormal weight is mixed with aqueous solution of nitric acid, heat this mixture, hydroxy nickel oxide is dissolved fully.The solution of gained with ICP apparatus for analyzing luminosity (for example VISTA-RL of VARIAN corporate system) analyzed thereafter.Like this, just can be in the hope of the part by weight of each contained in hydroxy nickel oxide metallic element (nickel, manganese etc.).
(B) utilize the mensuration of the average nickel valence mumber of redox titration method
Hydroxy nickel oxide is mixed with KI and sulfuric acid, stir this mixture fully, hydroxy nickel oxide is dissolved fully.The nickel ion that valence mumber is high in this course of dissolution, manganese ion etc. are oxidized to iodine with iodide ion, and this nickel ion and manganese ion etc. are reduced to divalent.So, the iodine that generated is carried out titration with the sodium thiosulfate solution of 0.1mol/L.According to the concentration and the titer thereof of sodium thiosulfate of this moment, can be in the hope of the total amount of aforesaid valence mumber greater than the nickel ion of divalent, manganese ion etc.
Use the value of above-mentioned valence mumber of trying to achieve, just can estimate the average valence mumber of the nickel in the hydroxy nickel oxide greater than the weight metal ratio of being tried to achieve among the total amount of the nickel ion of divalent, manganese ion etc. and above-mentioned (A).At this moment, the valence mumber with manganese contained in the hydroxy nickel oxide is assumed to 4 valencys.In hydroxy nickel oxide, contain under the situation of cobalt, the valence mumber of cobalt is assumed to 3.5 valencys.
In addition, in the present invention, the bulk density of hydroxy nickel oxide is preferably 2.15g/cm
3More than.The fillibility in shell of hydroxy nickel oxide is optimized.
In addition, the BET specific area of hydroxy nickel oxide is preferably 5～20m
2The scope of/g.The electrolyte dipping property of anode mixture is optimized.
In addition, preferably supported sodium ion at the particle surface of hydroxy nickel oxide.At this moment, sodium ion preferably accounts for 0.5～1 weight % of the total amount of hydroxy nickel oxide and sodium ion.
Hydroxy nickel oxide normally adds oxidant such as aqueous sodium hypochlorite solution in the nickel hydroxide in being scattered in sodium hydrate aqueous solution and makes and obtain.Thus, depend on the washing condition after the oxidation, supported sodium ion on the surface of hydroxy nickel oxide.When supporting in the amount of the sodium ion on the surface of hydroxy nickel oxide during more than 1 weight % of the total amount of hydroxy nickel oxide and sodium ion, then the harmful effect of sodium ion will become greatly, has battery behavior, mainly is the situation that preservation characteristics reduces.On the other hand, when the amount in its surperficial sodium ion of supporting during less than 0.5 weight %, the valence mumber that then is in the nickel of hydroxy nickel oxide skin section just reduces when discharge easily.Thus, have the situation that to obtain its capacity fully.
Support in the amount of the sodium ion on the surface of hydroxy nickel oxide and for example can try to achieve as followsly.
The nickel oxyhydroxide powder of ormal weight is mixed with aqueous solution of nitric acid,, this nickel oxyhydroxide powder is dissolved fully this mixture heating., the solution of gained with ICP apparatus for analyzing luminosity (for example VISTA-RL of VARIAN corporate system) analyzed, try to achieve the amount of sodium thereafter.Use this sodium amount to try to achieve the ratio (weight %) of sodium ion shared in the total amount of hydroxy nickel oxide and sodium ion.
In addition, described hydroxy nickel oxide preferably accounts for 10～80 weight % of anode mixture.When comparing as the manganese dioxide of positive active material and hydroxy nickel oxide, manganese dioxide is more good aspect the capacity of per unit weight or the density of filling in shell, material price.But for discharge voltage, strong load discharge characteristic etc., hydroxy nickel oxide is more good.Therefore, when considering the balance of cell integrated characteristic or price, most preferably the mixed proportion with the hydroxy nickel oxide in the anode mixture is made as above-mentioned scope.
Contained manganese dioxide in the anode mixture as alkaline battery of the present invention, the average grain diameter that preferably with the volume is benchmark is the electrolytic manganese dioxide about 30～50 μ m.
As conductive agent, can use graphite, various carbon black, fibrous carbon etc.In the middle of them, as conductive agent, the average grain diameter that most preferably with the volume is benchmark is the powdered graphite about 5～20 μ m.This is because make anodal particle easily, is difficult for having problems in addition when battery is made.In addition, by using such graphite, can be with the battery behavior stabilisation.Here, so-called graphite is meant crystallinity carbon, is meant the face (d at interval that utilizes (002) face that powder X-ray diffractometry tries to achieve
002) be the following materials of 3.4 .
In addition, conductive agent preferably accounts for 3～10 weight % of anode mixture.This is because can improve the volume energy density of the active material in the anode mixture fully, guarantees that strong load discharge characteristic is satisfactory.
Embodiment
Below, will the present invention is described in detail based on embodiment.
(making of hydroxy nickel oxide)
In the reactive tank that has possessed paddle, supply with nickelous sulfate (II) aqueous solution, manganese sulfate (II) aqueous solution, sodium hydrate aqueous solution and the ammoniacal liquor of normal concentration respectively continuously with pump with ormal weight.The solution of being supplied with is mixed continuously, is stirred in reactive tank, has separated out the nickel hydroxide particle.Make the pH of the reaction solution in the reactive tank reach 12, temperature reaches 50 ℃.Then, with the washing of nickel hydroxide particle and the vacuumize of separating out.In synthetic nickel hydroxide, the total amount that the content of manganese contained in the nickel hydroxide is adjusted into respect to metal ion contained in the nickel hydroxide reaches 5mol%.The nickel hydroxide that so obtains is made as nickel hydroxide a (Ni
0.95Mn
0.05(OH)
2).
In addition, replace manganese sulfate (II) aqueous solution except having used zinc sulfate (II) aqueous solution, cobaltous sulfate (II) aqueous solution or calcium nitrate (II) aqueous solution, identical method when utilizing with the above-mentioned nickel hydroxide a of making has been made nickel hydroxide b (Ni respectively
0.95Zn
0.05(OH)
2), nickel hydroxide c (Ni
0.95Co
0.05(OH)
2), nickel hydroxide d (Ni
0.95Ca
0.05(OH)
2).
In addition, except the mixed aqueous solution that has used zinc sulfate (II) and cobaltous sulfate (II) replaced manganese sulfate (II) aqueous solution, identical method when utilizing with the above-mentioned nickel hydroxide a of making had been made nickel hydroxide e (Ni
0.95Zn
0.025Co
0.025(OH)
2).
In addition, except not using manganese sulfate (II) aqueous solution, identical method when utilizing with the above-mentioned nickel hydroxide a of making has been made the not nickel hydroxide f of any metallic element of solid solution.
Use powder X-ray diffractometry to analyze the nickel hydroxide a～f that so obtains.Consequently can confirm: nickel hydroxide a～f has the crystal structure (ratio of β type is 100%) of β type, and the metallic element that is added among nickel hydroxide a～e is present in the nickel hydroxide crystal with the state of solid solution.Utilize laser diffraction formula particles distribution instrument (the microtrack FRA of Nikkiso Company Limited) to these nickel hydroxides a～f be that the average grain diameter of benchmark is measured with the volume, the result is about 10 μ m.Utilize sedimentating density measuring device (the Tap denser KYT-4000 of SEISHIN enterprise of Co., Ltd. system) that their bulk density is measured, the result is about 2.2g/cm
3In addition, utilize BET specific area measuring device (ASAP-2010 of Shimadzu Scisakusho Ltd's system) that their BET specific area is measured, the result is 10～12m
2/ g.
And, in following embodiment, be that average grain diameter, bulk density and the BET specific area of benchmark also is to use above-mentioned device to measure with the volume.
Then, the nickel hydroxide a of 200g is dropped into the sodium hydrate aqueous solution (concentration is 0.1mol/L) of 1L, when stirring, add the aqueous sodium hypochlorite solution as oxidant (effective chlorine density is 10wt%) of ormal weight, made reaction solution.Further stir this reaction solution, a is converted into hydroxy nickel oxide with nickel hydroxide.At this moment, the temperature with reaction solution is made as 50 ℃.
If necessary MIN theoretical amount is made as 1.0 equivalents in the time of will making nickel contained in the nickel hydroxide be oxidizing to 3.0 valencys, then the amount of the aqueous sodium hypochlorite solution that added is made as two kinds of 1.1 equivalents and 1.8 equivalents.In addition, be made as two kinds of 2.0 hours and 6.0 hours with having dropped into the processing time behind the aqueous sodium hypochlorite solution (mixing time).Like this, under as shown in table 14 different oxidizing conditions, 4 kinds of hydroxy nickel oxides have been made.
Then, the hydroxyl oxidize nickel particles of gained is washed.At this moment, wash the pH that proceeds to its filtrate and reach 11.5 (25 ℃).Hydroxy nickel oxide washing after 60 ℃ following vacuumizes 24 hour, obtained hydroxy nickel oxide A1～A4 thereafter.
Measured the amount of the sodium ion that the surface supported of these hydroxy nickel oxides.Consequently, the amount of this sodium ion is about the 0.8 weight % of total amount of hydroxy nickel oxide and sodium ion.
[table 1]
| Hydroxy nickel oxide | Processing time | The amount of aqueous sodium hypochlorite solution |
| A1 | 2.0 hour | 1.1 equivalent |
| A2 | 2.0 hour | 1.8 equivalent |
| A3 | 6.0 hour | 1.1 equivalent |
| A4 | 6.0 hour | 1.8 equivalent |
Then, except having used nickel hydroxide b～f, use method identical when making above-mentioned hydroxy nickel oxide A1～A4, made hydroxy nickel oxide B1～B4, C1～C4, D1～D4, E1～E4 and F1～F4 respectively.Here, represent that the A～F of each hydroxy nickel oxide is corresponding with nickel hydroxide a～f.In addition, if 1～4 numbering is identical with each numbering of the A1～A4 shown in the table 1, then expression is what to make under identical oxidizing condition.
These 24 kinds of hydroxy nickel oxides be the average grain diameter (D of benchmark with the volume
50) all be about 10 μ m.In addition, the bulk density of these hydroxy nickel oxides is about 2.3g/cm
3, the BET specific area is in 10～15m
2The scope of/g.
In addition, for these 24 kinds of hydroxy nickel oxides, measured the average valence mumber of its nickel.Its result is shown in the table 2.
In addition, utilize powder X-ray diffractometry, confirmed that any hydroxy nickel oxide all is the crystal structure based on the β type.That is to say, the intensity of the diffraction maximum of distinctive (003) face estimates that then the ratio of the crystal of β type is more than 98% in each hydroxy nickel oxide in the crystal structure of the intensity of the diffraction maximum of distinctive in the crystal structure according to the β type (001) face and γ type.But, owing to represent the sample at the peak of nickel hydroxide in addition, therefore read near the height of the diffraction maximum of (100) face the angle of diffraction 2 θ that are reflected in nickel hydroxide amount not oxidized and residual when utilizing oxidant to handle=33.8 °.Its result is shown in the table 2.In addition, " N.D. " is meant the meaning of the diffraction maximum that does not show (100) face in the table 2.In addition, the kind with the element of solid solution in hydroxy nickel oxide is shown in the table 2.
[table 2]
| Hydroxy nickel oxide | The kind of the element of solid solution | The average valence mumber of nickel | (100) height of the diffraction maximum of face |
| A1 | Mn | 2.95 | N.D. |
| A2 | Mn | 2.99 | N.D. |
| A3 | Mn | 2.98 | N.D. |
| A4 | Mn | 3.01 | N.D. |
| B1 | Zn | 2.75 | 280 |
| B2 | Zn | 2.86 | 195 |
| B3 | Zn | 2.83 | 75 |
| B4 | Zn | 2.99 | N.D. |
| C1 | Co | 2.96 | N.D. |
| C2 | Co | 2.99 | N.D. |
| C3 | Co | 2.98 | N.D. |
| C4 | Co | 3.02 | N.D. |
| D1 | Ca | 2.71 | 310 |
| D2 | Ca | 2.85 | 205 |
| D3 | Ca | 2.82 | 220 |
| D4 | Ca | 2.97 | N.D. |
| E1 | Zn and Co | 2.88 | 150 |
| E2 | Zn and Co | 2.94 | 35 |
| E3 | Zn and Co | 2.92 | 50 |
| E4 | Zn and Co | 3.00 | N.D. |
| F1 | Do not have | 2.85 | 155 |
| F2 | Do not have | 2.91 | 55 |
| F3 | Do not have | 2.92 | 50 |
| F4 | Do not have | 2.95 | N.D. |
For nickel contained among nickel hydroxide a or the c, even the amount of aqueous sodium hypochlorite solution is few, the processing time is short, also its average valence mumber can be oxidizing to about 3.0 valencys.So explanation, solid solution the nickel hydroxide a of manganese or solid solution the easy oxidation of nickel hydroxide c of cobalt.
In contrast, for nickel contained among nickel hydroxide b, d, e and the f, if do not add too much aqueous sodium hypochlorite solution, and do not carry out long time treatment, then its average valence mumber can not arrive near 3.0 valencys.This has just illustrated: for solid solution the nickel hydroxide b of zinc, solid solution the nickel hydroxide d of calcium, solid solution the nickel hydroxide e or other the nickel hydroxide f of metallic element of solid solution not of zinc and cobalt, oxidation is not easy to carry out.Here, particularly in nickel hydroxide b, d and e, solid solution in nickel hydroxide zinc ion or the valence mumber of calcium ion still be that divalent is constant.When nickel hydroxide is carried out oxidation with oxidant because these ions keep the state of divalents, therefore can think be difficult to oxidized.
(making of alkaline battery)
Use the nickel oxyhydroxide powder A1～F4 that obtains as described above, made alkaline battery as shown in Figure 1.
(making of anode mixture)
At first, will be with the volume average grain diameter of benchmark be the electrolytic manganese dioxide of 40 μ m, above-mentioned hydroxy nickel oxide A1, as the Delanium of conductive agent (the SP level of Japanese graphite Industrial Co., Ltd system; Average grain diameter is 15 μ m) mix at 50: 45: 5 with weight ratio, obtained mixed-powder.In per 100 weight portions of this mixed-powder, mix the potassium hydroxide aqueous solution of 1 weight portion, 40 weight %, this mixture is mixed with blender, obtained having the shot-like particle of the granularity of regulation.With the shot-like particle extrusion forming of gained is hollow circle tube, has made anode mixture.
(making of negative pole)
To be 2.5: 100: 200 mixed with weight ratio as the Sodium Polyacrylate of gelating agent, alkaline electrolyte and as the zinc powder of negative electrode active material, make gelled negative electrode.As alkaline electrolyte, used the potassium hydroxide aqueous solution of 40 weight %.
(assembling of alkaline battery)
Use the anode mixture and the gelled negative electrode that obtain as described above, made the alkaline battery of list 3 sizes as shown in Figure 1.
As anodal shell, used the shell of making by the steel plate of nickel plating.Inwall at this positive pole shell has formed the graphite applying film.
To the inside of this positive pole shell, insert a plurality of above-mentioned anode mixtures, thereafter,, make it to contact closely with the inner face of anodal shell by this anode mixture is pressurizeed once more.
Then, the hollow bulb to the inboard of this anode mixture has inserted barrier film and insulator cap., to battery case in inject electrolyte, make barrier film and anode mixture moistening thereafter.Here, as electrolyte, used the potassium hydroxide aqueous solution of 40 weight %.
After the injection of electrolyte, filled above-mentioned gelled negative electrode in the inboard of barrier film.Hush panel and base plate by integrated negative electrode collector inserted in gelled negative electrode thereafter.The open end of anodal shell is carried out ca(u)lk across hush panel and base plate, the peristome of anodal shell is sealed.At last, use outer dress label to cover the outer surface of anodal shell, finished battery.The battery of gained is made as battery A1.
Except having used hydroxy nickel oxide A2～A4, B1～B4, C1～C4, D1～D4, E1～E4 and F1～F4 with the replacement hydroxy nickel oxide A1, manufacture method during with making battery A1 is identical, has made battery A2～A4, B1～B4, C1～C4, D1～D4, E1～E4 and F1～F4.Here, battery B1～B4, C1～C4, D1～D4, E1～E4 and F1～F4 are the comparison batteries.
(evaluation of battery)
(low load discharge characteristic)
With each battery of 24 kinds of above-mentioned made under 20 ℃ with the constant current continuous discharge of 50mA, measured first discharge capacity when cell voltage reaches final voltage 0.9V (below be also referred to as " discharge capacity under the 50mA " or " low load discharge capacity ").
(strong load discharge characteristic)
With each above-mentioned 24 kinds battery constant current continuous discharge with 1000mA under 20 ℃, measured first discharge capacity when cell voltage reaches final voltage 0.9V (below be also referred to as " discharge capacity under the 1000mA " or " strong load discharge capacity ").
(preservation characteristics)
Will be in the constant current continuous discharge with 1000mA under 20 ℃ of the battery of preserving for 1 week under 60 ℃, measured discharge capacity when cell voltage reaches final voltage 0.9V (below be also referred to as " discharge capacity after the preservation ").The value that discharge capacity after preserving is represented with percent value with respect to the ratio of above-mentioned strong load discharge capacity is as the capacity sustainment rate.
The result of gained is shown in the table 3.In the table 3, low load discharge capacity and strong load discharge capacity are used as respectively with respect to the percent value of the value of low load discharge capacity that compares battery F4 and high capacity discharge capacity to be represented.
[table 3]
| Low load discharge capacity | Strong load discharge capacity | Preserved the capacity sustainment rate (%) after 1 week under 60 ℃ | |
| Battery A1 | 101 | 101 | 77 |
| Battery A2 | 103 | 102 | 78 |
| Battery A3 | 102 | 102 | 78 |
| Battery A4 | 103 | 103 | 80 |
| Compare battery B1 | 88 | 83 | 70 |
| Compare battery B2 | 95 | 93 | 75 |
| Compare battery B3 | 94 | 91 | 74 |
| Compare battery B4 | 97 | 97 | 75 |
| Compare battery C1 | 100 | 97 | 73 |
| Compare battery C2 | 100 | 97 | 75 |
| Compare battery C3 | 101 | 97 | 74 |
| Compare battery C4 | 102 | 98 | 75 |
| Compare battery D1 | 85 | 80 | 72 |
| Compare battery D2 | 94 | 91 | 76 |
| Compare battery D3 | 92 | 90 | 76 |
| Compare battery D4 | 98 | 97 | 76 |
| Compare battery E1 | 94 | 91 | 70 |
| Compare battery E2 | 97 | 95 | 74 |
| Compare battery E3 | 96 | 95 | 73 |
| Compare battery E4 | 98 | 98 | 75 |
| Compare battery F1 | 94 | 92 | 52 |
| Compare battery F2 | 96 | 95 | 61 |
| Compare battery F3 | 97 | 97 | 62 |
| Compare battery F4 | 100 (benchmark) | 100 (benchmark) | 65 |
In battery A1～A4, no matter be low load discharge capacity, strong load discharge capacity or preserve after the capacity sustainment rate, all demonstrated good value.Shown in low load discharge capacity and the high reason of strong load discharge capacity are thought as follows.That is, because the nickel valence mumber of hydroxy nickel oxide A1～A4 is enough high, so the discharge capacity of hydroxy nickel oxide becomes big.In addition, when manganese dioxide discharges after the discharge of hydroxy nickel oxide, as solid solution the effect of manganese, the conductivity of hydroxy nickel oxide is kept than the highland, and also can obtain enough capacity from manganese dioxide.
In addition, though the mechanism that preservation characteristics is enhanced is also uncertain, yet can think, because the manganese of solid solution in the crystal of hydroxy nickel oxide, oxygen generation overvoltage on the hydroxy nickel oxide is risen, consequently suppressed self discharge, so the capacity sustainment rate has demonstrated higher value.
On the other hand, for having used the average valence mumber of nickel not improved fully and part contains battery B1～B3, D1～D3, E1～E3 and the F1～F3 of the hydroxy nickel oxide of unreacted nickel hydroxide, low load discharge capacity and strong load discharge capacity do not improve like that.
Containing by excessively adding aqueous sodium hypochlorite solution and carrying out among battery B4, the D4 and E4 of the hydroxy nickel oxide that long time treatment obtains, low load discharge capacity, strong load discharge capacity and capacity sustainment rate are compared with battery B1～B3, battery D1～D3 and battery E1～E3 respectively, and what make moderate progress.But these characteristics are all poor than battery A1～A4 of the present invention.
In the battery C1～C4 of hydroxy nickel oxide of cobalt that used solid solution, because the nickel valence mumber of hydroxy nickel oxide is enhanced, therefore low load discharge Capacity Ratio is higher.But because the influence of the cobalt of institute's solid solution, the oxidation-reduction potential of hydroxy nickel oxide reduces, and it is high like that therefore strong load discharge capacity does not become.
As mentioned above, contain aforesaid hydroxy nickel oxide A1, A2, A3 or A4 and manganese dioxide, just can seek the improvement of the high capacity and the retention of alkaline battery by making anode mixture.Found in addition because solid solution has manganese, made hydroxy nickel oxide, be that the oxidation processes of utilizing oxidant of nickel hydroxide becomes very easy from nickel hydroxide.
Here, the amount of manganese contained in the hydroxy nickel oxide and the state of this manganese are studied.
Feed speed to manganese sulfate (II) aqueous solution is adjusted, so that the content of manganese is 0.3mol%, 0.5mol%, 1mol%, 3mol%, 7mol%, 10mol% or 12mol% with respect to the total amount of metal ion contained in the nickel hydroxide, in addition, use the manufacture method identical to synthesize 7 kinds of different nickel hydroxides of content of manganese with nickel hydroxide a.They are made as nickel hydroxide m1～m7.
Utilize powder X-ray diffractometry that nickel hydroxide m1～m7 is analyzed, results verification these nickel hydroxides crystal structures of all having the β type, in addition, in this nickel hydroxide crystal, the manganese that solid solution is added to some extent.
Feed speed to manganese sulfate (II) aqueous solution is adjusted, so that the content of manganese is 3mol% or 7mol% with respect to the total amount of metal ion contained in the nickel hydroxide, and the pH of reaction solution is made as 11.0, the temperature of reaction solution is made as 40 ℃, in addition, use the manufacture method identical to make nickel hydroxide m8 and m9 with nickel hydroxide a.
Utilize powder X-ray diffractometry that nickel hydroxide m8 and m9 are analyzed.Here, as an example, the X-ray diffraction spectrum figure of nickel hydroxide m5 (Mn:7mol%, solid solution) (curve A) and nickel hydroxide m9 (Mn:7mol%, eutectic) (curve B) is shown among Fig. 2.
These nickel hydroxides m8 and m9 have the crystal structure of β type nickel hydroxide.But, as shown in Figure 2, in nickel hydroxide m9, the peak (position of the bullet of Fig. 2) of Mn oxide has appearred also being considered to.Can infer thus, in nickel hydroxide m8 and m9, manganese be not solid solution in the nickel hydroxide crystal, but be scattered in the nickel hydroxide with the form of Mn oxide, that is to say that the nickel hydroxide m8 and the m9 that contain manganese are eutectic.
In addition, nickel hydroxide m1～m9's is that the average grain diameter of benchmark is about 10 μ m with the volume, and bulk density is about 2.2g/cm
3, the BET specific area is 10～12m
2/ g.
Then, use the nickel hydroxide ml of 200g, the temperature of reaction solution is made as 50 ℃, the amount of the aqueous sodium hypochlorite solution that added is made as 1.5 equivalents, and will drop into the processing time behind the aqueous sodium hypochlorite solution (mixing time) and be made as 4.0 hours, in addition, use the method identical that nickel hydroxide m1 is converted into hydroxy nickel oxide with embodiment 1.
Thereafter, with resulting hydroxyl oxidize nickel particles washing.At this moment, wash the pH that proceeds to filtrate and reach 11.5 (25 ℃).Afterwards, the hydroxy nickel oxide after the washing 60 ℃ of following vacuumizes 24 hours, has been obtained hydroxy nickel oxide M1.
Except having used nickel hydroxide m2～m9 to replace the nickel hydroxide m1, use method identical when making hydroxy nickel oxide M1 to make hydroxy nickel oxide M2～M9.In addition, support in the amount of the sodium ion on the surface of hydroxy nickel oxide M1～M9 and be about the 0.8 weight % of total amount of hydroxy nickel oxide and sodium ion.
9 kinds of hydroxy nickel oxides of gained be the average grain diameter (D of benchmark with the volume
50) all be about 10 μ m.The bulk density of these hydroxy nickel oxides is about 2.3g/cm
3, the BET specific area is 10～15m
2/ g, the average valence mumber of nickel is about 3.0.
Use powder X-ray diffractometry that hydroxy nickel oxide M1～M9 is analyzed.Consequently, in these hydroxy nickel oxides, all do not see any residual nickel hydroxide.
Then, use above-mentioned hydroxy nickel oxide M1～M9, made alkaline battery M1～M9 in the same manner with the foregoing description 1.Here, battery M1 and battery M7～M9 are for comparing battery.
For the battery M1～M9 of making like this, use the method identical with embodiment 1 tried to achieve low load discharge capacity, strong load discharge capacity and preserve after the capacity sustainment rate.The result of gained is shown in the table 4.In table 4, identical with table 3, low load discharge capacity and strong load discharge capacity are represented as the percent value with respect to the value of low load discharge capacity that compares battery F4 and high capacity discharge capacity respectively.In addition, also expressed manganese shared amount (mol%) and state (solid solution or eutectic) thereof in the contained metallic element in hydroxy nickel oxide in the table 4.
[table 4]
| The amount of Mn in the hydroxy nickel oxide (mol%) and state thereof | Low load discharge capacity | Strong load discharge capacity | Preserved the capacity sustainment rate (%) after 1 week under 60 ℃ | |
| Compare battery M1 | 0.3, solid solution | 98 | 99 | 66 |
| Battery M2 | 0.5, solid solution | 101 | 101 | 71 |
| | 1, solid solution | 102 | 102 | 74 |
| | 3, solid solution | 103 | 102 | 77 |
| | 7, solid solution | 102 | 101 | 79 |
| | 10, solid solution | 101 | 101 | 80 |
| Compare battery M7 | 12, solid solution | 98 | 97 | 80 |
| Compare | 3, eutectic | 98 | 98 | 72 |
| Compare | 7, eutectic | 97 | 96 | 74 |
| Compare battery F4 | Do not have | 100 (benchmark) | 100 (benchmark) | 65 |
According to table 4, in the battery M2～M6 of the hydroxy nickel oxide that has used with the ratio solid solution of 0.5～10mol% manganese, no matter be which of low load discharge capacity, strong load discharge capacity, capacity sustainment rate, all demonstrated higher value.
On the other hand, in the battery M1 of the solid solution capacity that has used manganese as the hydroxy nickel oxide of 0.3mol%, these characteristic values have demonstrated low value.This is considered to can't obtain its effect of sufficient because the amount of manganese is very few.
In addition, in the battery M7 of the solid solution capacity that has used manganese as the hydroxy nickel oxide of 12mol%, owing to help the nickel content of battery capacity relatively to tail off, the value of therefore low load discharge capacity and strong load discharge capacity has reduced.
In addition, the hydroxy nickel oxide that contains manganese is among the battery M8 and M9 of eutectic, though the capacity sustainment rate demonstrates than higher value, the reduction of low load discharge capacity and strong load discharge capacity is remarkable.This is presumably because manganese does not embody following effect well in hydroxy nickel oxide M8 and M9, that is: by the manganese solid solution, then the conductivity in discharge latter stage of hydroxy nickel oxide can be kept than the highland, and from manganese dioxide, also can obtain enough capacity and make it high capacity.
In the present embodiment, the average grain diameter (granularity) of hydroxy nickel oxide is studied.
Change forms the feed speed of the ammoniacal liquor of agent as complex ion, with the size of the nucleus that is adjusted at the nickel hydroxide of separating out in the reactive tank and the speed of growth of nickel hydroxide particle, and is the average grain diameter (D of benchmark with the volume with nickel hydroxide
50) be made as 5 μ m, 8 μ m, 11 μ m, 15 μ m and 20 μ m respectively, in addition, use the manufacture method identical to make nickel hydroxide with nickel hydroxide a.Resulting nickel hydroxide is made as nickel hydroxide x1～x5 respectively.
Utilize powder X-ray diffractometry that nickel hydroxide x1～x5 is analyzed, the result shows the crystal structure that has the β type, and solid solution manganese.In addition, the bulk density of these nickel hydroxides is in 2.1～2.2g/cm
3Scope, the BET specific area is in 10～18m
2The scope of/g.
Then, use the nickel hydroxide x1 of 200g, the temperature of reaction solution is made as 50 ℃, the amount of the aqueous sodium hypochlorite solution that added is made as 1.5 equivalents, and will drop into the processing time behind the aqueous sodium hypochlorite solution (mixing time) and be made as 4.0 hours, in addition, use the method identical that nickel hydroxide x1 is converted into hydroxy nickel oxide with embodiment 1.
Thereafter, with resulting hydroxyl oxidize nickel particles washing.At this moment, wash the pH that proceeds to filtrate and reach 11.5 (25 ℃).Afterwards, the hydroxy nickel oxide after the washing 60 ℃ of following vacuumizes 24 hours, has been obtained hydroxy nickel oxide X1.
Except having used nickel hydroxide x2～x5 replacing the nickel hydroxide x1, use method identical when making hydroxy nickel oxide X1 to make hydroxy nickel oxide X2～X5 respectively.In addition, support in the amount of the sodium ion on the surface of hydroxy nickel oxide X1～X5 and be about the 0.8 weight % of total amount of hydroxy nickel oxide and sodium ion.
Measured the average grain diameter of above-mentioned hydroxy nickel oxide X1～X5.Consequently, hydroxy nickel oxide X1～X5 has the average grain diameter (D roughly the same with nickel hydroxide x1～x5 respectively
50).In addition, the bulk density of these hydroxy nickel oxides is in 2.2～2.3g/cm
3Scope, the BET specific area is in 10～20m
2The scope of/g.
The average valence mumber of contained nickel all is about 3.0 in these 5 kinds of hydroxy nickel oxides.
In addition, utilize powder X-ray diffractometry to measure having or not of nickel hydroxide.Consequently, in hydroxy nickel oxide X1～X5, do not see any residual nickel hydroxide.
Then, use above-mentioned hydroxy nickel oxide X1～X5, use the method identical to make alkaline battery X1～X5 with embodiment 1.Here, battery X1 and X5 are for comparing battery.
For each battery X1～X5 of making like this, measured low load discharge capacity, strong load discharge capacity and preserve after the capacity sustainment rate.The result of gained is shown in the table 5.In table 5, identical with table 3, low load discharge capacity and strong load discharge capacity are represented as the percent value with respect to the value of low load discharge capacity that compares battery F4 and high capacity discharge capacity respectively.In addition, also represent to have the average grain diameter (D of hydroxy nickel oxide contained in each battery in the table 5
50).
[table 5]
| Average grain diameter (the D of hydroxy nickel oxide 50) (μm) | Low load discharge capacity | Strong load discharge capacity | Preserved the capacity sustainment rate (%) after 1 week under 60 ℃ | |
| Compare | 5 | 99 | 99 | 67 |
| | 8 | 103 | 102 | 77 |
| Battery X3 | 11 | 103 | 103 | 79 |
| Battery X4 | 15 | 103 | 103 | 76 |
| Compare battery X5 | 20 | 100 | 99 | 66 |
| Compare | 10 | 100 (benchmark) | 100 (benchmark) | 65 |
As shown in table 5, using with the average grain diameter (D of volume as benchmark
50) be among the battery X2～X4 of hydroxy nickel oxide of scope of 8～15 μ m, any one in low load discharge capacity, strong load discharge capacity and the capacity sustainment rate all demonstrated high value.
On the other hand, the battery X1 that has used the little hydroxy nickel oxide to 5 μ m of average grain diameter, and average grain diameter greatly in the battery X5 of the hydroxy nickel oxide of 20 μ m, low load discharge capacity, strong load discharge capacity and capacity sustainment rate all do not obtain satisfied value.For the reason that produces such difference, though still very not clear and definite now, can consider as follows.That is be that the conductance of the particle that electrically contacts degree or associated company of anode mixture particle becomes poor under the situation of hydroxy nickel oxide of 5 μ m or 20 μ m, having used particle diameter.If particularly because when 60 ℃ 1 week of preservation, hydroxy nickel oxide carried out self discharge (conductivity of particle surface reduces) down, it is obvious that this situation will become.
And, though here do not describe in detail, yet in other experiment, even the average grain diameter of electrolytic manganese dioxide contained in the anode mixture is changed in the scope of 30～50 μ m, or the average grain diameter of graphite changed in the scope of 5～20 μ m, perhaps change the mixed proportion of hydroxy nickel oxide, the capacity sustainment rate after 60 ℃ of following 1 weeks of preservation of resulting battery also can be relevant with the average grain diameter of hydroxy nickel oxide.That is to say, can confirm a bit, that is, and by having used with the average grain diameter (D of volume as benchmark
50) be the hydroxy nickel oxide of 8～15 μ m, its capacity sustainment rate becomes good.
As mentioned above, found from guaranteeing the viewpoint of discharge capacity and retention that the scope that the average grain diameter of hydroxy nickel oxide is adjusted into 8～15 μ m is very important.
Embodiment 4
In the present embodiment, for the situation of the average valence mumber of nickel that obtains relevant hydroxy nickel oxide and test.
Use the nickel hydroxide a (Ni that makes among the embodiment 1
0.95Mn
0.05(OH)
2) 200g, the temperature of reaction solution is made as 50 ℃, the amount of the aqueous sodium hypochlorite solution that added is changed into 0.9 equivalent, 1.0 equivalents, 1.2 equivalents, 2.0 equivalents, 2.5 equivalents or 3.0 equivalents, and will drop into the processing time behind the aqueous sodium hypochlorite solution (mixing time) and be made as 6.0 hours, in addition, use the method identical that nickel hydroxide is converted into hydroxy nickel oxide with embodiment 1.
Then, with resulting 6 kinds of hydroxyl oxidize nickel particles washing.At this moment, wash the pH that proceeds to filtrate and reach 11.5 (25 ℃).Afterwards, the hydroxy nickel oxide after the washing 60 ℃ of following vacuumizes 24 hours, has been obtained hydroxy nickel oxide Y1～Y6.In addition, support in the amount of the sodium ion on the surface of hydroxy nickel oxide and be about the 0.8 weight % of total amount of hydroxy nickel oxide and sodium ion.
6 kinds of hydroxy nickel oxides that so obtain be the average grain diameter (D of benchmark with the volume
50) being about 10 μ m, bulk density is about 2.3g/cm
3, the BET specific area is 10～15m
2/ g.
Measured the average valence mumber of nickel contained in these hydroxy nickel oxides.The results are shown in Table 6.In addition, the addition of also having represented aqueous sodium hypochlorite solution in the table 6.
[table 6]
| Hydroxy nickel oxide | The amount of aqueous sodium hypochlorite solution | The average valence mumber of contained nickel in the hydroxy nickel oxide |
| Y1 | 0.9 equivalent | 2.89 |
| Y2 | 1.0 equivalent | 2.93 |
| Y3 | 1.2 equivalent | 2.95 |
| Y4 | 2.0 equivalent | 3.02 |
| Y5 | 2.5 equivalent | 3.05 |
| Y6 | 3.0 equivalent | 3.07 |
Then, use above-mentioned hydroxy nickel oxide Y1～Y6, use the method identical to make alkaline battery Y1～Y6 with the foregoing description 1.
For the battery Y1～Y6 of making like this, use the method identical with embodiment 1 measured low load discharge capacity, strong load discharge capacity and preserve after the capacity sustainment rate.The result of gained is shown in the table 7.In addition, in table 7, low load discharge capacity and strong load discharge capacity are expressed as the percent value with respect to the value of low load discharge capacity that compares battery F4 and high capacity discharge capacity respectively.
[table 7]
| Low load discharge capacity | Strong load discharge capacity | Preserved the capacity sustainment rate (%) after 1 week under 60 ℃ | |
| Battery Y1 | 98 | 98 | 73 |
| Battery Y2 | 100 | 99 | 77 |
| Battery Y3 | 101 | 101 | 79 |
| Battery Y4 | 103 | 103 | 80 |
| Battery Y5 | 103 | 102 | 80 |
| Battery Y6 | 103 | 98 | 80 |
| Compare battery F4 | 100 (benchmark) | 100 (benchmark) | 65 |
As shown in table 7, in the average valence mumber of nickel was battery Y3～Y5 of 2.95～3.05, any one in low load discharge capacity, strong load discharge capacity and the capacity sustainment rate all demonstrated high value.
In the average valence mumber of nickel was lower than 2.95 battery Y1 and Y2, because the capacity of the per unit weight of hydroxy nickel oxide tails off, so discharge capacity reduced slightly.
In the average valence mumber of nickel was higher than 3.05 battery Y6, strong load discharge capacity had reduced slightly.This be considered to because, when the valence mumber of nickel becomes extremely high, the cause that the ratio of inactive γ type structure increases in the hydroxy nickel oxide.
Like this, in the present invention, preferably the average valence mumber with nickel contained in the hydroxy nickel oxide is adjusted into 2.95～3.05 such scopes.
And because any one battery is all good aspect preservation characteristics, so these batteries have effect of sufficient especially in the purposes of paying attention to preservation characteristics.
In the present embodiment, the washing condition of hydroxy nickel oxide is studied.And, when changing the washing condition, support in the amount of the sodium ion of the particle surface of hydroxy nickel oxide and can change.
Use the nickel hydroxide a (Ni that makes among the embodiment 1
0.95Mn
0.05(OH)
2) 200g, the temperature of reaction solution is made as 50 ℃, the amount of the aqueous sodium hypochlorite solution that added is made as 1.5 equivalents, and will drop into the processing time behind the aqueous sodium hypochlorite solution (mixing time) and be made as 4.0 hours, in addition, use the method identical that nickel hydroxide is converted into hydroxy nickel oxide with embodiment 1.
Then, with resulting hydroxyl oxidize nickel particles washing.At this moment, reach moment of 12.5,12.0,11.5,11.0 or 10.5 at the pH of filtrate (25 ℃) and finish washing.Each hydroxy nickel oxide after the washing 60 ℃ of following vacuumizes 24 hours, has been obtained supporting the different hydroxy nickel oxide W1～W5 of amount in the sodium ion on surface.
Average grain diameter (the D of 5 kinds of hydroxy nickel oxide W1～W5 that so obtain
50) all be about 10 μ m.In addition, the bulk density of these hydroxy nickel oxides is about 2.3g/cm
3, the BET specific area is in 10～15m
2The scope of/g.
Measured the amount that supports in the sodium ion on the surface of each hydroxy nickel oxide.The results are shown in Table 8.The pH of the filtrate when in addition, having represented the washing of hydroxy nickel oxide in the table 8.
[table 8]
| Hydroxy nickel oxide | The pH of the filtrate during washing | Support amount (weight %) in the sodium ion of hydroxyl oxidize nickel surface |
| W1 | 12.5 | 1.42 |
| W2 | 12.0 | 0.98 |
| W3 | 11.5 | 0.76 |
| W4 | 11.0 | 0.51 |
| W5 | 10.5 | 0.39 |
Then, use above-mentioned hydroxy nickel oxide W1～W5, use the method identical to make alkaline battery W1～W5 with the foregoing description 1.
Use the battery W1～W5 that so makes, use the method identical with embodiment 1 measured low load discharge capacity, strong load discharge capacity and preserve after the capacity sustainment rate.The result of gained is shown in the table 9.In addition, in the table 9, low load discharge capacity and strong load discharge capacity are expressed as the percent value with respect to the value of low load discharge capacity that compares battery F4 and high capacity discharge capacity respectively.
[table 9]
| Low load discharge capacity | Strong load discharge capacity | Preserved the capacity sustainment rate (%) after 1 week under 60 ℃ | |
| Battery W1 | 101 | 100 | 69 |
| Battery W2 | 103 | 103 | 77 |
| Battery W3 | 103 | 102 | 78 |
| Battery W4 | 102 | 101 | 77 |
| Battery W5 | 100 | 100 | 72 |
| Compare battery F4 | 100 (benchmark) | 100 (benchmark) | 65 |
As shown in table 9, be 11.0～12.0 and support in the amount of its surperficial sodium ion and be among the battery W2～W4 of scope of 0.5～1 weight % of total amount of hydroxy nickel oxide and sodium ion that at the pH of the filtrate in when washing any one in low load discharge capacity, strong load discharge capacity and the capacity sustainment rate all demonstrates high value.
On the other hand, supporting in the battery W1 of amount more than 1 weight % of the sodium ion on surface, the grow that influences as impurity of sodium ion is that the battery performance at center reduces with the preservation characteristics.In addition, supporting in the battery W5 of amount less than 0.5 weight % of the sodium ion on surface, how low load discharge capacity and high capacity discharge capacity are not enhanced.This is presumably because following cause: because the amount of sodium ion is few, therefore the valence mumber of the nickel of hydroxy nickel oxide skin section reduces easily when discharge, and consequently capacity is not obtained fully.
In the present embodiment, the mixed proportion of the hydroxy nickel oxide in the anode mixture is studied.
The average grain diameter that will be benchmark with the volume is the hydroxy nickel oxide A4 that makes in the electrolytic manganese dioxide, the foregoing description 1 of 40 μ m and Delanium (the SP level of Japanese graphite Industrial Co., Ltd system, average grain diameter is 15 μ m) mix with 10 kinds of part by weight shown in the table 10, obtained mixed-powder.Except using these mixed-powders, use the method identical to make alkaline battery Z1～Z10 with embodiment 1.Here, battery Z1 and Z10 are for comparing battery.
Use the battery Z1～Z10 that so makes, use the method identical to measure low load discharge capacity and strong load discharge capacity with embodiment 1.The result of gained is shown in the table 10.In addition, in the table 10, low load discharge capacity and strong load discharge capacity are expressed as the percent value with respect to the value of low load discharge capacity that compares battery F4 and high capacity discharge capacity respectively.In addition, represented to compare the mixed proportion of electrolytic manganese dioxide, hydroxy nickel oxide and graphite contained in the anode mixture of battery F4 in the table 10.
[table 10]
| Mixed proportion in the anode mixture (weight %) | Low load discharge capacity | Strong load discharge capacity | |||
| Electrolytic manganese dioxide | Hydroxy nickel oxide | Graphite | |||
| Compare battery Z1 | 95 | 0 | 5 | 108 | 81 |
| Battery Z2 | 90 | 5 | 5 | 107 | 92 |
| Battery Z3 | 85 | 10 | 5 | 106 | 101 |
| Battery Z4 | 80 | 15 | 5 | 106 | 102 |
| Battery Z5 | 65 | 30 | 5 | 104 | 103 |
| Battery Z6 | 30 | 65 | 5 | 103 | 104 |
| Battery Z7 | 15 | 80 | 5 | 101 | 105 |
| | 10 | 85 | 5 | 98 | 105 |
| | 5 | 90 | 5 | 96 | 106 |
| Compare battery Z10 | 0 | 95 | 5 | 95 | 106 |
| Compare battery F4 | 50 | 45 | 5 | 100 (benchmark) | 100 (benchmark) |
As shown in table 10, in battery Z8, the Z9 and Z10 of ratio more than 80 weight % of hydroxy nickel oxide A4, low load discharge capacity descends to some extent.In the battery Z1 and Z2 of ratio less than 10 weight % of hydroxy nickel oxide A4, strong load discharge capacity descends to some extent.According to above result as can be known, in order to form low load discharge capacity and the strong all good battery of load discharge capacity, in anode mixture, preferably contain 10～80 weight % amount solid solution the hydroxy nickel oxide of manganese.
In addition because battery Z1～Z10 is good aspect at least one of strong load discharge capacity or low load discharge capacity, therefore by use with the corresponding purposes of their speciality in, can obtain the effect of these batteries fully.
In the present embodiment, the mixed proportion as the graphite of conductive agent in the anode mixture is studied.
Is mixing in 1: 1 with the hydroxy nickel oxide A4 that makes among employed electrolytic manganese dioxide among the embodiment 1 and the embodiment 1 with weight ratio.The graphite that uses in wherein adding embodiment 1 makes graphite shared part by weight in anode mixture reach 6 kinds of values as shown in table 11, thereby has obtained 6 kinds of mixed-powders.Except using these mixed-powders, use the method identical to make alkaline battery U1～U6 with embodiment 1.
Use the battery U1～U6 that so makes, use the method identical to measure low load discharge capacity and strong load discharge capacity with embodiment 1.The result of gained is shown in the table 11.In addition, in table 11, low load discharge capacity and strong load discharge capacity are expressed as the percent value with respect to the value of low load discharge capacity that compares battery F4 and high capacity discharge capacity respectively.In addition, represented to compare the amount of graphite contained in the anode mixture of battery F4 in the table 11.
[table 11]
| Graphite shared ratio (weight %) in anode mixture | Low load discharge capacity | Strong load discharge | |
| Battery U1 | |||
| 2 | 101 | 100 | |
| | 3 | 102 | 101 |
| | 5 | 103 | 103 |
| | 8 | 102 | 103 |
| | 10 | 101 | 104 |
| Battery U6 | 12 | 97 | 102 |
| Compare | 5 | 100 (benchmark) | 100 (benchmark) |
As shown in Table 11, when the ratio of graphite contained in the anode mixture was 3～10 weight %, particularly flash-over characteristic was good.In the battery U1 of mixed proportion less than 3 weight % of graphite, because the conductive network in the anode mixture is incomplete, therefore particularly strong load discharge capacity decreases slightly.In the battery U6 of mixed proportion greater than 10 weight % of graphite, because therefore the ratio step-down relatively of the active material in the anode mixture can think that its energy density reduces in low load discharge.According to above result, in the present invention, conductive agent preferably is contained in the anode mixture with the amount of 3～10 weight %.
In addition, battery U1～U6 compares with battery F4 relatively all more good aspect, by using in the purposes corresponding with their speciality, no matter uses which of these batteries U1～U6, can obtain effect of sufficient.
In addition, in the foregoing description, about solid solution the hydroxy nickel oxide of manganese, having used its bulk density is 2.2～2.3g/cm
3, the BET specific area is 10～20m
2The material of/g.When the packed density in battery case of the nickel oxyhydroxide powder of manganese of having considered solid solution, its bulk density is preferably 2.15g/cm
3More than, during the dipping of the electrolyte of the anode mixture in considering battery, the BET specific area is preferably 5～20m
2The scope of/g.
In the above-described embodiments, though used hydroxy nickel oxide with the independent solid solution of manganese, even use except manganese and also solid solution than the hydroxy nickel oxide of elements such as the zinc of manganese less amount, cobalt, also can obtain roughly the same result.
In addition, in the above-described embodiments, though used graphite as conductive agent, under the situation that various carbon blacks or fibrous carbon is used alone as conductive agent or with them, mix with graphite under the situation about using, also can obtain basic effect of the present invention.
In addition, in the anode mixture particle that has disposed tubular in the anodal shell of drum of made, barrier film, gelled negative electrode etc. so-called the zinc beyond the alkaline battery of carbon type, the present invention can also be applicable in the battery of other structures such as alkaline coin shape, square in the foregoing description.
According to the present invention, the alkaline battery that can provide capacity height, preservation characteristics to be enhanced.This alkaline battery for example can be used for the power supply that portable electric appts is used.
Claims (5)
1, a kind of alkaline battery, it possess anode mixture, negative pole and be disposed at described anode mixture and described negative pole between barrier film, wherein,
Described anode mixture contains hydroxy nickel oxide, manganese dioxide and conductive agent, wherein,
(1) in the described hydroxy nickel oxide at least solid solution manganese is arranged, described manganese accounts for 0.5～10mol% of the total amount of metallic element contained in the described hydroxy nickel oxide,
(2) described hydroxy nickel oxide is based on the crystal structure of β type,
(3) described hydroxy nickel oxide is that the average grain diameter of benchmark is 8～15 μ m with the volume.
2, alkaline battery according to claim 1, wherein, described hydroxy nickel oxide further satisfies at least a in the following rerum natura:
(4) the average valence mumber of nickel is 2.95～3.05;
(5) bulk density is 2.15g/cm
3More than;
(6) the BET specific area is 5～20m
2/ g.
3, alkaline battery according to claim 1, wherein, described hydroxy nickel oxide has supported sodium ion on its surface, and described sodium ion accounts for 0.5～1 weight % of the total amount of described hydroxy nickel oxide and described sodium ion.
4, alkaline battery according to claim 1, wherein, described hydroxy nickel oxide accounts for 10～80 weight % of described anode mixture.
5, alkaline battery according to claim 1, wherein, described conductive agent is a graphite, described graphite accounts for 3～10 weight % of described anode mixture.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004301153 | 2004-10-15 | ||
| JP301153/2004 | 2004-10-15 | ||
| JP355690/2004 | 2004-12-08 |
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|---|---|
| CN1957490A true CN1957490A (en) | 2007-05-02 |
| CN100499217C CN100499217C (en) | 2009-06-10 |
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|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106463694A (en) * | 2014-03-28 | 2017-02-22 | 杜拉塞尔美国经营公司 | Beta-delithiated layered nickel oxide electrochemically active cathode material and a battery including said material |
| CN109643797A (en) * | 2016-08-29 | 2019-04-16 | 株式会社田中化学研究所 | Sodium ion secondary battery positive active material |
-
2005
- 2005-09-20 CN CNB2005800165198A patent/CN100499217C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106463694A (en) * | 2014-03-28 | 2017-02-22 | 杜拉塞尔美国经营公司 | Beta-delithiated layered nickel oxide electrochemically active cathode material and a battery including said material |
| CN106463694B (en) * | 2014-03-28 | 2020-01-14 | 杜拉塞尔美国经营公司 | Beta-delithiated layered nickel oxide electrochemically active cathode material and battery comprising said material |
| CN110911633A (en) * | 2014-03-28 | 2020-03-24 | 杜拉塞尔美国经营公司 | β -delithiated layered nickel oxide electrochemically active cathode material and battery comprising said material |
| CN109643797A (en) * | 2016-08-29 | 2019-04-16 | 株式会社田中化学研究所 | Sodium ion secondary battery positive active material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100499217C (en) | 2009-06-10 |
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