CN1260837C - Alkali storage battery and hydrogen absorbing alloy electrode for use therein - Google Patents
Alkali storage battery and hydrogen absorbing alloy electrode for use therein Download PDFInfo
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Abstract
The present inventive hydrogen absorbing alloy electrode having a conductive core material and, supported thereby, an active material layer containing a hydrogen absorbing alloy powder, wherein the alloy powder has a shape selected from among a sphere, a shape near sphere and an egg shape, and the core material comprises a conductive sheet and, bound to the surface thereof, a sintered nickel object of a fibrous or cylindrical shape, or wherein the active material layer comprises an active material layer A containing an alloy powder A having an average particle diameter a supported by the core material and, supported by the active material layer A, an active material layer B containing an alloy powder B having an average particle diameter b (provided that a < b), or wherein the active material layer further comprises a mechanically pulverized alloy powder having at least one selected from nickel and cobalt on the surface thereof. The hydrogen absorbing alloy electrode can be used for manufacturing an alkali storage battery which is excellent not only in discharge characteristics, but also in cycle life.
Description
Technical field
The present invention relates to alkaline battery and used hydrogen-occlussion alloy electrode thereof.
Background technology
The alkaline battery of employing hydrogen-storage alloy is widely used as the power supply of various wireless devices and electronic equipment.Particularly nickel-hydrogen dattery is safe from harm to environment, has high-energy-density.Therefore, nickel-hydrogen dattery is hopeful as must be with the electrical source of power of the electric tool or the electric automobile of high current charge-discharge, perhaps as the stand-by power supply that requires long-term reliability.
The used hydrogen-storage alloy of nickel-hydrogen dattery-as adopt the part of Ni the CaCu that has with metal replacements such as Co, Mn, Al
5The MmNi of type crystal structure
5It is alloy.Here, Mm represents lucium.
Hydrogen-storage alloy adopts the manufacturings such as atomization that molten alloy is injected the casting of mold, the roller quench that molten alloy is flowed into carry out chilling between two rolls, molten alloy is dripped the centrifugal spray method on the disk of high speed rotating and molten alloy is sprayed to inert gas.
For the alloy that casting and roller-way quench are obtained is used for the electrode of nickel-hydrogen dattery, must utilize the suction storage of mechanical means or hydrogen and emit step, be ground into the following particle diameter of 100 μ m.And the employing atomization owing to can obtain fine spherical alloy powder, does not therefore need pulverising step.
Utilize the shaggy alloy powder that breaking method obtains will micronizing, but spherical alloy powder have uniform alloy structure, will suppress micronized and carry out along with charge and discharge cycles.In addition, spherical alloy powder is owing to littler than the specific area of pulverizing alloy powder, so corrosion resistance might as well.Spherical alloy powder is compared with pulverizing alloy powder as described in the Japanese patent laid-open 3-116655 communique, can be with the high density filling electrode.
According to above-mentioned reason, the spherical alloy powder of therefore main employing.But the specific area of spherical alloy powder is little, and the contact between alloy powder particle and alloy powder are the some contact with the contacting of conductive core material of electrode.Therefore, adopt the electrode of spherical alloy powder to compare with adopting the situation of pulverizing alloy powder, the problem of existence is the current collection ability.Figure 1 shows that the existing electrode generalized section that adopts spherical alloy powder.As shown in Figure 1, the conductive core material 1 of electrode is the some contact with contacting of spherical alloy powder 2.
In view of the foregoing, in Japanese patent laid-open 11-97002 communique, proposed spherical alloy powder is mixed the method for using with the pulverizing alloy powder.In addition, in Japanese patent laid-open 11-283618 communique, proposed to have by pulverizing the double-deck electrode that alloy powder constitutes one deck and is made of one deck spherical alloy powder.Promptly, adopt simultaneously and pulverize alloy powder and spherical alloy powder in order to improve the current collection ability of electrode.
But, pulverize alloy powder and compare, along with the easy micronizing of increase of charge and discharge cycles number with spherical alloy powder.Therefore, the current collection ability that contains the electrode of pulverizing alloy powder descends gradually.In addition, because micronizing, the surface area of the feasible alloy powder that contacts with electrolyte increases, so the component of alloy is dissolved, has consumed electrolyte for no reason.The problem that the result exists is that the internal resistance of cell rises, perhaps flash-over characteristic and cycle characteristics variation.
The present invention makes in order to solve such problem, and purpose is to provide all excellent alkaline battery in flash-over characteristic and cycle characteristics two aspects and used hydrogen-storage alloy thereof.
Summary of the invention
Ganoid spherical (comprising similarly shape such as approximate spherical and the egg-shape) hydrogen-storage alloy powder that utilizes atomization or centrifugal spray method to make is difficult to micronizing.In addition, spherical alloy powder is compared with the shaggy alloy powder that utilizes mechanical crushing method to make, because specific area is little, therefore is not vulnerable to the corrosion of alkaline electrolyte.But if adopt spherical alloy powder, then existing problems are that the conductive core material of electrode is insufficient with contacting of alloy powder, flash-over characteristic decline.Therefore, the present invention provides and improves contacting of conductive core material and spherical alloy powder, the alkaline battery that flash-over characteristic and cycle characteristics two aspects are all excellent.
The hydrogen-occlussion alloy electrode that the present invention relates to, be by conductivity core and the electrode that utilizes the active material layer that contains hydrogen-storage alloy powder of described core support to constitute, that described alloy powder has is spherical, selected any shape in the approximate spherical and egg-shape, described core by conductive sheet and with described conductive sheet surface on the fiber that combines or the sintrered nickel of column constitute.
The hydrogen-occlussion alloy electrode that the invention still further relates to, be by conductivity core and the electrode that utilizes the active material layer that contains hydrogen-storage alloy powder of described core support to constitute, spherical, approximate spherical and selected any shape of egg-shape kind that described alloy powder has, described core has at length direction and forms many at interval, and above-below direction is the mesh sheets of the slit of approximate diamond opening.
The invention still further relates to the autofrettage of hydrogen-occlussion alloy electrode, this method has three steps, i.e. many slits of step (1) on conductive sheet are provided with the coupling part shorter than slit at interval at the length direction of described sheet material, form staggered shape; Step (2) is at the Width of described sheet material, and the part that adjacent slots is clamped alternately encircles up and down, make described slit up and down direction be approximate diamond opening, by obtaining mesh sheets like this; Step (3) has the hydrogen-storage alloy powder of selected any shape in spherical, approximate spherical and the egg-shape to described mesh sheets filling.
The invention still further relates to hydrogen-occlussion alloy electrode, be the active material layer A of the hydrogen-storage alloy powder A that contains average grain diameter a that supports by the conductivity core and by described core and the hydrogen-storage alloy powder B that contains average grain diameter b that supported by described active material layer A active material layer B (here, the electrode that a＜b) constitutes, described alloy powder A and B have any shape of selecting respectively from spherical, approximate spherical and egg-shape.
The thickness A d of described active material layer A is preferably Ad: Bd=1 with the ratio of the thickness B d of described active material layer B: 9～3: 7.
The average grain diameter a of best described alloy powder A is 5～20 μ m, and the average grain diameter b of described alloy powder B is 25～50 μ m.
The invention still further relates to the autofrettage of hydrogen-occlussion alloy electrode, have three steps, wherein step (1) is to utilize atomization or centrifugal spray method, make hydrogen-storage alloy powder A respectively and have the hydrogen-storage alloy powder B (a＜b), of the average grain diameter b of selected any shape in spherical, approximate spherical and the egg-shape here with average grain diameter a of selected any shape in spherical, approximate spherical and the egg-shape; Step (2) is the paste A that modulation contains described alloy powder A, coating paste A on the conductivity core; Step (3) is the paste B that modulation contains described alloy powder B, coating paste B on described paste A.
Described step (1) can adopt following step, promptly makes the hydrogen-storage alloy powder with particle size distribution, with the alloy powder screening that the obtains described alloy powder B for the described alloy powder A of average grain diameter a and average grain diameter b.
The invention still further relates to hydrogen-occlussion alloy electrode, be by conductivity core and the electrode that constituted by the active material layer that contains hydrogen-storage alloy powder that described core is supported, described alloy powder is spherical by having, the alloy powder C of selected any shape and the alloy powder D that utilizes mechanical crushing to obtain constitute in the approximate spherical and egg-shape, have selected at least a material in nickel and the cobalt on the surface of described alloy powder D.
Surface at described alloy powder C also can have at least a material of selecting in nickel and the cobalt.
Best described alloy powder C has following particle diameter of 90 μ m and the average grain diameter of 20～40 μ m, and described alloy powder D has the average grain diameter of 10～15 μ m.
The weight Cw of the described alloy powder C that described active material layer contains is preferably Cw: Dw=80 with the ratio of the weight Dw of described alloy powder D: 20～95: 5.
The invention still further relates to the autofrettage of hydrogen-occlussion alloy electrode, have three steps, wherein step (1) is to utilize atomization or centrifugal spray method, makes the hydrogen-storage alloy powder C with selected any shape in spherical, approximate spherical and the egg-shape; Step (2) is to utilize mechanical crushing method, makes shaggy hydrogen-storage alloy powder D; Step (3) is the paste that modulation contains described alloy powder C and D, the described paste of coating on the conductivity core.
The invention still further relates to the alkaline battery that is made of positive pole, negative pole, barrier film (separator) and alkaline electrolyte, described negative pole is above-mentioned any hydrogen-occlussion alloy electrode.
Description of drawings
Fig. 1 is for adopting the existing electrode generalized section of spherical alloy powder.
The part stereogram of the conductivity core that Fig. 2 constitutes for conductive sheet and with the sintrered nickel of the fibrous or column of the surface combination of aforementioned conductive sheet.
Fig. 3 is the top view of the conductive sheet of the staggered slit of formation.
The profile of the conductivity core of Fig. 4 approximate diamond opening slit for above-below direction has.
Fig. 5 is active material layer B with the spherical hydrogen-storage alloy powder B that contains average grain diameter b that supports by the active material layer A of the spherical hydrogen-storage alloy powder A that contains average grain diameter a of conductivity core support and by active material layer A (the hydrogen-occlussion alloy electrode profile of a＜b) here.
Figure 6 shows that the charge and discharge cycles number of the battery A～D that obtains among the embodiment 1 and the graph of a relation of battery capacity.
Figure 7 shows that the active material layer A ' thickness proportion of battery E1～E5 that embodiment 3 obtains and the graph of a relation of discharge capacity and cycle characteristics.
Figure 8 shows that the alloy powder average grain diameter that the active material layer A ' of the battery E6～E10 that obtains among the embodiment 4 is used and the graph of a relation of discharge capacity and cycle characteristics.
Figure 9 shows that the alloy powder average grain diameter that the active material layer B ' of the battery E11～E17 that obtains among the embodiment 5 is used and the graph of a relation of discharge capacity and cycle characteristics.
Concrete example
Example 1
The hydrogen-occlussion alloy electrode that this example relates to, be by conductivity core and the electrode that constituted by the active material layer that contains hydrogen-storage alloy powder that described core is supported, that described alloy powder has is spherical, selected any shape in the approximate spherical and egg-shape, and described core constitutes by conductive sheet and with the fibrous or granular sintrered nickel of described conductive sheet surface combination.
The conductive sheet that constitutes the conductivity core can be used metallic plate metal forming etc.Conductive sheet also can be bored a hole.
Figure 2 shows that the part stereogram of an example of above-mentioned conductivity core.
Fibrous or column sintrered nickel 3 extends to the thickness direction of core from the surface of the conductive sheet 4 of perforation, so core has three-dimensional structure.Because spherical hydrogen-storage alloy powder remains in the gap of such sintrered nickel easily, so the contact point of alloy powder and conductivity core increases the current collection path increase in the electrode.In addition, also can suppress alloy powder takes place from the situation that core comes off.By constituting alkaline battery, can access the alkaline battery of high rate discharge flash-over characteristic and cycle characteristics excellence with this electrode.
Adopt the vertical structure of sintrered nickel fibrous or column, can only form the current collection path at the thickness direction of conductivity core.With above-mentioned different be, adopt the sintrered nickels of many fibrous or columns near end separately, to twine mutually or the structure of combination, owing to also can form the current collection path at the in-plane of conductive sheet, so the resistance of electrode further reduces, and flash-over characteristic further improves.
Sintrered nickel fibrous or column is preferably thick more the closer to the end.If adopt the core with such sintrered nickel, then the resistance of electrode top layer part reduces, and polarization reduces, and charge-discharge characteristic further improves.In addition, because the mechanical strength of electrode top layer part improves, therefore the alloy powder confining force in electrode top layer part also improves.
Adopt the method for the following stated, can make conductive sheet have the sintrered nickel of fibrous or column.
At first, at the surface coated binding agent of conductive sheet.Then, with conductive sheet ground connection, will utilize charged cover (hood) to make its charged resin fibre little by little give the conductive sheet surface.Charged resin fibre is attached to the surface of conductive sheet to the Surface Vertical of conductive sheet with fiber end.In the binding agent drying, resin fibre is fixed on after the surface of conductive sheet, utilize electroless plating on resin fibre, to form the nickel film, make it have conductivity.Electroplate then, until the nickel film reaches specific thickness.Because the closer to the end of resin fibre, electric charge is concentrated more, current density is high more, so the nickel film also becomes thick more.The resin fibre with nickel film that is fixed on the conductive sheet is carried out sintering, can access desirable conductivity core.In the top layer of the core that obtains with this method part, the diameter of sintrered nickel is thicker.
In said method, it is the regenerated celulose fibre of 1～5mm that resin fibre preferably adopts average diameter dimension 5～50 μ m, average length.
The nickel amount that covers resin fibre fixing on the conductive sheet of unit are is preferably 290～310g/m
2
The average diameter of the sintrered nickel of fibrous or column is preferably 5～70 μ m.In addition, the average length of sintrered nickel is preferably 1～5mm.In addition, the specific area of the conductive sheet of anchoring fiber shape or column sintrered nickel is preferably 10～50m
2/ g.The surface that sintrered nickel is preferably in conductive sheet roughly uniformly-spaced is provided with.
If strengthen the sintrered nickel amount of fibrous or column, then compare with the existing core that constitutes by metal porous bodies such as foaming metal sheets, can obtain the bigger conductivity core of specific area.Thereby the contact area of hydrogen-storage alloy powder and the core of the sintrered nickel with fibrous or column is greater than the contact area of hydrogen-storage alloy powder and foaming metal, and the current collection ability also has raising.
Active material layer by the support of above-mentioned conductivity core contains the hydrogen-storage alloy powder that has from spherical, approximate spherical and any shape that egg-shape is selected.It is alloy that hydrogen-storage alloy preferably adopts the MmNi5 that in the past always adopted.Spherical hydrogen-storage alloy powder can utilize atomization or the centrifugal spray method known to obtain in the past.The average grain diameter of alloy powder is preferably 15～30 μ m.
Active material layer is to be coated on the conductivity core by the paste that will contain alloy powder to form.Except alloy powder, can also mix tackifier, conductive agent, binding agent and dispersant etc. in the paste.Pole plate shapings after the slurry coating etc. are as long as utilize well-known in the past method.
Example 2
This example relates to hydrogen-occlussion alloy electrode, be by conductivity core and the electrode that constituted by the active material layer that contains hydrogen-storage alloy powder that described core is supported, any shape that described alloy powder has is spherical, select in the approximate spherical and egg-shape, described core has at length direction and forms some at interval, and above-below direction is the mesh sheets of the slit of approximate diamond opening.
Mesh sheets as described above can utilize following method to obtain.
At first,, the coupling part shorter than slit is set at interval, forms staggered shape in the sheet length direction for many slits on the conductive sheet.Conductive sheet can adopt metallic plate or metal forming etc.
Figure 3 shows that the top view of the conductive sheet that forms staggered shape slit.In Fig. 3, the length of each slit 5 is preferably the coupling part 6 that 0.5～2mm, slit 5 are provided with 0.2～1mm length, is staggered shape, forms conductive sheet 1.The interval that each bar is adjacent is preferably 0.1～0.5mm.
Then, at the Width of aforementioned sheet material, the part that adjacent slots is clamped alternately encircles up and down, make aforementioned slots up and down direction be approximate diamond opening.
Figure 4 shows that above-below direction is the conductivity core profile of the slit of approximate diamond opening.Utilization goes out part 7 to the arch of core thickness direction, and the opening portion of approximate rhombus forms in a straight line, so this core has three-dimensional structure.Spherical hydrogen-storage alloy powder remains on the slit position that above-below direction is approximate diamond opening easily.Therefore, the contact point of alloy powder and core increases, and the current collection path in the electrode increases.In addition, also can suppress alloy powder comes off from core.By constituting alkaline battery, can access the alkaline battery of efficient electric rate flash-over characteristic and cycle characteristics excellence with this electrode.
The active material layer of being supported by above-mentioned conductivity core is identical with example 1.
Example 3
The hydrogen-occlussion alloy electrode of this example can describe with reference to its section shown in Figure 5.In Fig. 5, support contains the active material layer A (8a) of the hydrogen-storage alloy powder A (2a) of average grain diameter a on the conductivity core 1.In addition, go up to support to contain active material layer B (the 8b) (a＜b), of the hydrogen-storage alloy powder B (2b) of average grain diameter b here at active material layer A (8a).Alloy powder A (2a) and B (2b) have any shape of selecting respectively from spherical, approximate spherical and egg-shape.
In above-mentioned electrode, the little alloy powder A of average grain diameter contacts with the conductivity core relatively.At the big alloy powder B of its outside relative average grain diameter of configuration.Like this, contact with the conductivity core, can increase current collection and count by making the little alloy powder A of average grain diameter.Thereby, even adopt spherical alloy powder, there is not alloy particle as shown in Figure 1 to contact inadequate situation with the conductivity core yet, can suppress flash-over characteristic and descend.
Because the specific area of the alloy powder A that average grain diameter is little is big, therefore be subjected to the corrosion of electrolyte easily.So, the thickness of active material layer A can fully guarantee with scope that core contacts in, preferably to approach as far as possible.According to this viewpoint, the thickness A d of active material layer A is preferably Ad: Bd=1 with the ratio of the thickness B d of aforementioned active material layer B: 9～3: 7.
The average grain diameter a of alloy powder A is according to fully guaranteeing to be preferably the viewpoint that alloy powder and contacting of conductivity core are counted below the 20 μ m.In addition, if the average grain diameter of alloy powder A is too small, then the alloy corrosion reaction will significantly be carried out, and therefore be preferably more than the 5 μ m.Promptly have the alloy powder A of 5～20 μ m average grain diameters, can guarantee sufficient current collection path, make alkaline electrolyte that the corrosion of alloy is reached bottom line simultaneously by employing.
In addition, the average grain diameter b of alloy powder B is preferably 25～50 μ m.If the average grain diameter b of alloy powder B is less than 20 μ m, then because particle diameter is too small, hydrogen storage capacity reduces, and therefore causes electrode capacity to reduce, and alloy corrosion is also quickened.In addition, if average grain diameter surpasses 50 μ m, then, therefore discharge and recharge reaction and reduce because response area reduces.
The following describes the autofrettage of above-mentioned electrode.
At first, utilize atomization or centrifugal spray method to make the hydrogen-storage alloy powder A of average grain diameter a and the hydrogen-storage alloy powder B of average grain diameter b (a＜b), respectively here.Utilize atomization or centrifugal spray method, can access have any shape of selecting in spherical, the approximate spherical and egg-shape, metal structure evenly, specific area is less than the alloy powder of pulverizing alloy powder, excellent corrosion resistance.
Here, in order to change the average grain diameter of alloy powder, as long as change the temperature of molten alloy or the synthesis conditions such as ejection pressure when molten alloy sprayed in inert gas.In addition, also can make hydrogen-storage alloy powder, the alloy powder that obtains is filtered into the alloy powder A of average grain diameter a and the alloy powder B of average path b with particle size distribution.Though this method needs the equipment of screening usefulness,, therefore have and to stablize the advantage of making because the synthesis condition of alloy is fixed.
Then, modulate the paste B that contains the paste A of alloy powder A and contain alloy powder B.As long as the paste modulation is according to the method that adopted in the past.Then, the paste A that at first will contain the little alloy powder A of relative average grain diameter is coated on the conductivity core with always well-known methods such as slit methods, makes the paste drying of coating with warm braw.Then, coating contains the paste B of the bigger alloy powder B of relative average grain diameter, any drying of carrying out on paste A.Like this, can form the active material layer that constitutes by desirable different types of layer.The moulding of the pole plate after the paste coating etc. need only with well-known method.
Example 4
This example relates to hydrogen-occlussion alloy electrode, be by conductivity core and the electrode that utilizes the active material layer that contains hydrogen-storage alloy powder of described core support to constitute, described alloy powder is spherical by having, the alloy powder C of selected any shape and the alloy powder D that utilizes mechanical crushing method to obtain constitute in the approximate spherical and egg-shape, and the surface of described alloy powder D has selected at least a material in nickel and the cobalt.
Be this example by adopting ganoid spherical alloy powder C and shaggy pulverizing alloy powder D simultaneously, the current collection ability of electrode is improved, again by surface, suppress to constitute the dissolving of element and separate out with specific metal covering alloy powder D.In addition, so-called in the present invention " coverings " not necessarily refers to the uniform one deck of formation, also comprises special metal attached to the state of alloy surface etc.
As the metal on the surface of cover pulverizing alloy powder D, so long as, form cover layer, have the component that can suppress alloy and be dissolved in that the materials with function of situation gets final product in the alkaline electrolyte effectively attached to the alloy powder surface.For example, preferably adopt at least a material of in nickel that alloy surface also works as catalyst and cobalt, selecting.
In this example, as long as cover the surface of pulverizing alloy powder D with metal at least, but the surface of spherical alloy powder C is effective with at least a material covering of nickel and cobalt also.This is because though have oligodynamical to separate out from spherical alloy powder C, the situation of component dissolving is arranged also.
Alloy powder C preferably has following particle diameter of 90 μ m and the average grain diameter of 20～40 μ m.This be because, have the alloy particle that surpasses 90 μ m particle diameters, along with charge and discharge cycles, micronizing easily reduces cycle characteristics.In addition, less than 20 μ m, then the hydrogen storage capacity of alloy particle reduces as if average grain diameter, and the corrosion of alloy powder C is quickened.In addition, if average grain diameter surpasses 40 μ m, then because the response area of alloy powder C reduces, therefore the reactivity that discharges and recharges reduces.
In addition, alloy powder D preferably has the average grain diameter of 10～15 μ m.Rule of thumb know and pulverize alloy powder, reach the degree of average grain diameter 15 μ m along with charge and discharge cycles produces micronizing.Therefore, by adopting the pulverizing alloy powder with such particle diameter in advance, to suppress further micronizing, this is effective for preventing that cycle characteristics from worsening.
Alloy powder C in the electrode and the weight ratio of alloy powder D be preferably 80: 20～and 95: 5, promptly all 5～20 weight % of hydrogen-storage alloy powders pulverize alloy powder D.This be because, if the weight ratio of alloy powder D surpasses 20 weight %, then be difficult to the more alloy powder of electrode filling, can not obtain sufficient characteristic, if less than 5 weight %, then contact insufficiently between alloy particle or between alloy particle and conductivity core, flash-over characteristic can not improve.
The following describes object lesson of the present invention.
Embodiment 1
The manufacturing of battery A (1) hydrogen-storage alloy
Ratio of components in accordance with regulations weighs each raw material such as commercially available Mm (rare earth alloys), Ni, Co, Mn and Al, utilizes high-frequency induction heating dissolving stove to dissolve.In inert gas, from the crucible of molten alloy is housed, molten alloy is dropped on the disk with the 20000rpm high speed rotating each time slightly, surpass chilling, make spherical MmNi
3.55Co
0.75Mn
0.40Al
0.30Alloy powder.Spherical alloy powder carries out 1 hour heat treatment in being controlled in 900 ℃ electric furnace.In addition, be spherical alloy powder to be carried out 1 hour heat treatment in the present embodiment with 900 ℃, if but can suppress the suitable temperature and time of segregation, then other conditions also can.
The alloy powder that obtains is the very neat and well spaced spherical particle of average grain diameter 50 μ m, utilizes the uniformity of the resulting alloy structure of elementary analysis fabulous, and hydrogen storage capacity is also excellent.
(2) manufacturing of alloy paste
With above-mentioned alloy powder heat stir to the potassium hydroxide aqueous solution of 80 ℃ proportion 1.30, dipping 60 minutes, then wash, till making the pH value of cleaning water reach below 10.
Then, with the alloy powder after cleaning in 60 ℃ pH value is 3.0 aqueous acetic acid, stir, dipping 30 minutes, then wash, till the pH value that makes clean water reached more than 6, obtaining with water was the hydrogen-storage alloy powder slurries of dispersant.
To the per 100 weight portion alloy powders of these slurries add 0.15 weight portion carboxymethyl cellulose as tackifier, as 0.3 weight portion carbon black of conductive agent and as 0.8 parts by weight of styrene butadiene copolymer of binding agent, mix, make the alloy paste.
(3) making of conductivity core
Prepare the iron porous metals of the nickel plating of thick 0.06mm, aperture 2mm, aperture opening ratio 52%.Two sides at aforementioned porous metals is that binding agent (solid constituent 20%) is with porous metals ground connection with gunite coating phenol.
In addition, prepare the staple fibre of diameter 15 μ m is cut off the fine hair of growth 4mm.One side makes this fine hair charged with charged cover, simultaneously it is bit by bit fallen from sieve, and the two sides attached to the porous metals of ground connection makes it towards vertical direction.After the binding agent drying, fine hair is fixing on the porous metals sheet, and one side attracts with ventilating fan then, and one side is brushed with the fine hair that rotating brush will not bond.The fixing fine hair amount of the unit are of the part that comprises the hole of porous metals is 15g/m
2
Utilize electroless plating to form the nickel film to fixing fine hair, then electroplate, the nickel film is reached till the 2 μ m.Then, utilize sintering to remove floss removing, obtaining the surface, to have average diameter be that 18 μ m, average length are the conductivity core of sintrered nickel of the fibrous or column of 4mm.The fixing sintrered nickel amount of the unit are of the part that comprises the hole of porous metals is 75g/m
2In addition, to have the specific area of the conductivity core of sintrered nickel be 30m on the surface
2/ g.
(4) making of electrode
To the aforementioned alloy paste of aforementioned conductivity core filling, carry out drying and pressurization, form active material layer.Surface at active material layer covers with the fluorine resin powder.Then, cut off pole plate, obtain the hydrogen-occlussion alloy electrode of wide 35mm, long 150mm, thick 0.4mm, capacity 2200mAh.
(5) making of battery
The hydrogen-occlussion alloy electrode that obtains and well-known sintered nickel positive electrode across sulfonated polyolefin system nonwoven fabrics barrier film, are rolled into helical form, constitute the pole plate group.After the pole plate group inserted metal shell, the ratio that rises with 40g/ of injecting ormal weight is dissolved in the electrolyte that the potassium hydroxide aqueous solution of proportion 1.30 is made with lithium hydroxide, and was with hush panel that shell upper is airtight then.By like this, obtain the hermetic type nickel-hydrogen dattery A of 4/5A size, nominal capacity 1500mAh.
Battery B
Prepare the iron rectangular sheet material of thick 0.06mm.This sheet material is sent into patrix between counterdie, and this patrix and counterdie are multi-disc have been formed the tabular cutter that many slits form the knife edge part of usefulness form across predetermined distance is overlapping.Then, aforementioned patrix and counterdie towards the relative direction driving of advancing and retreat, by forming many slits in the length direction compartment of terrain of rectangular sheet material like this, and are staggered.When advancing and retreat driving with aforementioned patrix and counterdie towards relative direction, the part that adjacent slots is clamped alternately encircles up and down, makes aforementioned slots form the opening of approximate rhombus at above-below direction.Then, sheet material is electroplated, the nickel film is reached till the 2 μ m, obtain mesh sheets.The thickness of mesh sheets is 0.4mm.
Here, the length of each slit is 0.5mm, and the longitudinal separation between slit (length of coupling part) is 0.2mm, is 0.1mm in the slit adjacent spaces of sheet width direction.
As the conductivity core, in addition, make the hydrogen-occlussion alloy electrode identical with this mesh sheets with battery A.The electrode that obtains is wide 35mm, long 150mm, thick 0.5mm and capacity 2200mAh.Make the battery B identical with this electrode with battery A.
Battery C
With the iron porous metals of the nickel plating of thick 0.06mm, aperture 2mm, aperture opening ratio 52% directly as the conductivity core, in addition, the electrode that make the hydrogen-occlussion alloy electrode identical with battery A, obtains is wide 35mm, long 150mm, thick 0.4mm and capacity 2200mAh.Make the battery C identical with this electrode with battery A.
Battery D
Ratio of components in accordance with regulations weighs each raw material such as commercially available Mm (rare earth alloys), Ni, Co, Mn and Al, utilizes high-frequency induction heating dissolving stove to dissolve.After making the molten alloy cooling, utilize mechanical means that the alloy pig that obtains is pulverized, obtaining average grain diameter is the pulverizing alloy powder of 30 μ m.Except pulverize alloy with this, make the hydrogen-occlussion alloy electrode identical with battery A.The electrode that obtains is wide 35mm, long 150mm, thick 0.4mm and capacity 2200mAh.Make the electrode D identical with this electrode with electrode C.
The evaluation of battery A～D
(1) discharge capacity
With the charging of the current value of 1C after 72 minutes, the current value discharge with 0.2C or 3C reaches till the 1.0V cell voltage with battery.Table 1 is depicted as the discharge capacity and the average discharge volt of each battery at this moment.
Table 1
| Battery | Discharge capacity (mAh) (average discharge volt (V)) | |
| 0.2C | 3C | |
| A | 1500 (1.25) | 1120 (1.10V) |
| B | 1500 (1.25) | 1070 (1.10) |
| C | 1470 (1.24) | 960 (1.06) |
| D | 1500 (1.25) | 1030 (1.10) |
As shown in table 1, if relatively battery A, B and battery C, D, then with the low rate discharge characteristic approximately equal of 0.2C.But with the high-frequency electrical rate flash-over characteristic of 3C, then battery A, B compare with battery C, D, its discharge capacity and average discharge volt excellence.This be because, the conductivity core of battery A, B utilizes the sintrered nickel or the network structure of fibrous or column, then the contact-making surface of alloy particle and core connects increase, current collection path increase.
In addition, the high rate discharge flash-over characteristic of battery C, D is because it adopts common porous metals as the conductivity core, and is therefore low than battery A, B.This be because, alloy particle lacks the current collection ability with the contact point of core than battery A, B.In addition, the high rate discharge flash-over characteristic of battery C is also poorer than battery D.This be because, therefore battery C adopts spherical alloy powder, compares with adopting the battery D that pulverizes alloy powder, between alloy particle or be disadvantageous aspect the contact point between alloy particle and core.
(2) cycle characteristics
With battery under 20 ℃ with the charging of the current value of 1C, reach theoretical capacity 120% till, with the current value discharge of 3C, cell voltage is reached till the 1.0V again, repeat above-mentioned such circulation.Figure 6 shows that at this moment the charge and discharge cycles number and the relation of battery capacity.
As shown in Figure 6, battery A, B compare with battery C, D, and cycle characteristics improves.
As its reason, at first adduciblely be in battery A, B, to adopt and suppress to constitute that the element dissolving is separated out, the spherical alloy powder of excellent corrosion resistance.Secondly adduciblely be,, utilize the sintrered nickel or the network structure of fibrous or column for the conductivity core of battery A, B, the easy filling of alloy powder, the contact point of alloy powder and conductivity core increase as a result can suppress alloy powder and peel off from core.
In addition, battery C, D be owing to adopt common porous metals as the conductivity core, so alloy powder peels off from core easily, destroys contacting between alloy particle and core or alloy particle easily.Thereby the cycle characteristics of battery C, D reduces.In addition, battery D dissolves the pulverizing alloy powder of separating out or corroding easily easily owing to adopt structure to go out element, therefore compares with battery C, and cycle characteristics is also poor.
Battery E
(1) manufacturing of hydrogen-storage alloy
Ratio of components in accordance with regulations weighs commercially available Mm (rare earth alloys), Ni, Mn, Al and Co, in inert gas atmosphere, utilizes high-frequency induction heating dissolving stove to dissolve.The dissolving alloy that obtains is dripped from the below of crucible, the high pressure argon gas to this molten alloy spraying, is obtained spherical alloy powder.The alloy powder that obtains carries out 1 hour heat treatment in being controlled to 900 ℃ electric furnace.
The alloy powder composition that obtains is analyzed, and the result is MmNi
3.55Mn
0.4Al
0.3Co
0.75, alloy structure is extremely uniform.In addition, the shape of powder particle is confirmed, shown it is ganoid spheroid.
The alloy powder that obtains is screened, and obtaining average grain diameter is the alloy powder C ' of 30 μ m.In addition, the part of alloy powder C ' is carried out classification, being divided into average grain diameter is alloy powder A ' and the remaining alloy powder B ' of 10 μ m.
(2) making of alloy paste
With alloy powder A ' heat stir to the potassium hydroxide aqueous solution of 80 ℃ proportion 1.30 under, flood 60 minutes, then wash, make the pH value of clean water reach below 10 till.
Then, under the alloy powder after cleaning stirred in 60 ℃ pH value is 3.4 aqueous acetic acid, flooded 20 minutes, then wash, make the pH value of clean water reach more than 6 till, obtaining with water is the hydrogen-storage alloy powder slurry of dispersant.
To the per 100 weight portion alloy powder A ' of this slurry add 0.15 weight portion carboxymethyl cellulose as tackifier, as 0.3 weight portion carbon black of conductive agent and as 0.8 parts by weight of styrene butadiene copolymer of binding agent, mix, make alloy paste A '.
Except adopting alloy powder B ' replacement alloy powder A ', all the other are same as described above, make alloy paste B '.
(3) manufacturing of electrode
Aforementioned alloy paste A ' is coated on the porous metals as the conductivity core, carries out drying, form active material layer A '.Then, go up the aforementioned alloy paste B ' of coating, carry out drying, form active material layer B ' at active material layer A '.Then, to the two-layer active material layer pressurization of supporting by core, at surface coverage fluorine resin powder.
Making the part by weight of the contained alloy powder B ' of contained alloy powder A ' of active material layer A ' and active material layer B ' is 2: 8.Then, cut off pole plate, obtain the hydrogen-occlussion alloy electrode of wide 35mm, long 150mm, thick 0.4mm, capacity 2200mAh.
(4) manufacturing of battery
The hydrogen-occlussion alloy electrode that obtains and well-known sintered nickel positive electrode across nylon system nonwoven fabrics barrier film, are rolled into helical form, constitute the pole plate group.After the pole plate group inserted metal shell, that injects ormal weight was dissolved in the electrolyte that the potassium hydroxide aqueous solution of proportion 1.30 is made with the ratio of 40g/l with lithium hydroxide, with hush panel that shell upper is airtight then.By like this, obtain the hermetic type nickel-hydrogen dattery E of 4/5A size, nominal capacity 1500mAh.
Battery F
Except using alloy powder C ' to replace the situation of alloy powder A ', with top described same making alloy paste C ', this alloy paste C ' coated on the perforated metal dry, pressurize, form the active material layer that one deck constitutes.At this active material layer surface coated fluororesin powder., cut off pole plate, obtain the hydrogen-occlussion alloy electrode of wide 35mm, long 150mm, thick 0.4mm, capacity 2200mAh thereafter.Except the situation of using this electrode, make the battery F the same with battery E.
Battery G
Ratio of components in accordance with regulations weighs each raw material such as commercially available Mm (rare earth alloys), Ni, Co, Mn and Al, utilizes high-frequency induction heating dissolving stove to dissolve.With the MmNi that consists of that obtains after the molten alloy cooling
3.55Mn
0.4Al
0.3Co
0.75Alloy pig after 1 hour, carry out waterproof pulverization with 1100 ℃ of heat treatments, obtaining average grain diameter is the alloy powder D ' of 30 μ m.
Except using alloy powder D ' replacement alloy powder A ', all the other are identical with the situation of battery E, make alloy paste D '.Replace alloy paste A ' with alloy paste D ', form the active material layer A that supports by the conductivity core ", replace alloy paste B ' with alloy paste C ', at active material layer A " go up form active material layer B ".In addition, make the battery G identical with battery E.
Battery H
Except adopting alloy powder C ' with alloy powder D ' mixes the mixture that obtains at 2: 8 with weight ratio, all the other are same as described above, make alloy paste E.E is coated on the porous metals with the alloy paste, carries out drying and pressurization, forms the active material layer that is made of one deck.Then, make the battery H identical with battery F.
The evaluation of battery E～H
(1) discharge capacity
With battery under 20 ℃ with current value 1.5A charging, reach theoretical capacity 120% till, again under 0 ℃ with current value 4.5A discharge, cell voltage is reduced till the 1.0V, try to achieve discharge capacity at this moment.The discharge capacity of battery F as 100, is represented the discharge capacity of each battery with relative value in table 2.The relative value of discharge capacity is preferably more than 110.
(2) cycle characteristics
With battery under 20 ℃ with current value 1.5A charging, reach theoretical capacity 120% till, with current value 1.5A discharge, cell voltage is reached till the 1.0V again, repeat above-mentioned such circulation.Then, try to achieve 80% the period that discharge capacity is reduced to initial capacity.The period of battery F as 100, is represented the period of each battery with relative value at table 2.The relative value of period is so long as more than 90, can think passable.
Table 2
| Battery | The average grain diameter of alloy (μ m) | Discharge capacity | Cycle characteristics | |
| The A layer | The | |||
| E | ||||
| 10 | 30 | 118 | 97 | |
| | 30 | 100 | 100 | |
| | 30 | 30 | 120 | 82 |
| | 30 | 122 | 78 | |
In table 2, battery E have contact with core contain the little spherical alloy A of average grain diameter ' active material layer A ', with the active material layer B ' that contains the big spherical alloy of average grain diameter to support on it, the flash-over characteristic among the battery E is improved largely than battery F.This be because, the minimizing of the contact resistance of core and alloy.In addition, battery E is owing to the pulverizing alloy powder that does not contain corrosion-resistant, so cycle characteristics is better than containing the battery G and the H that pulverize alloy powder.
Embodiment 3
The thickness that makes active material layer A ' is 0～5% with respect to the ratio of the two layers of thickness that active material layer A ' and active material layer B ' constitute, and in addition, makes the battery E1～E5 identical with battery E.Here, the average grain diameter of the used hydrogen-storage alloy powder of active material layer A ' and active material layer B ' is fixed as 10 μ m and 30 μ m respectively.
Then, identical with embodiment 2, try to achieve 80% the period that the discharge capacity of each battery and discharge capacity are reduced to initial capacity.And, with the thickness proportion of active material layer A ' be the discharge capacity of 0% battery E1 and discharge capacity be reduced to initial capacity 80% period as 100, try to achieve the relative value of E2～E5.The thickness that Figure 7 shows that active material layer A ' is with respect to the ratio of two layers of thickness and the relation of discharge capacity and cycle characteristics.
According to Fig. 7 as can be known, be 0% battery E1, be 10% battery E2, be 20% battery E3 and be 30% battery E3, can access good cycle characteristics for the thickness proportion of active material layer A '.This be because, the thickness proportion of active material layer A ' is little, the alloy powder content that its average grain diameter is little is few, can suppress alloy corrosion.In addition, surpass at 10% o'clock in the thickness proportion of active material layer A ', discharge capacity increases considerably.This be because, the reduction of the contact resistance of alloy and core.We can say that according to this result the thickness proportion of active material layer A ' is preferably 10～30%.
Embodiment 4
The average grain diameter that makes the used alloy powder of active material layer A ' is 1～25 μ m, in addition, makes the battery E6～E10 identical with battery E.Here, the average grain diameter of the alloy powder that active material layer B ' is used is fixed as 30 μ m, and the part by weight of the alloy powder that alloy powder that active material layer A ' is contained and active material layer B ' are contained was fixed as 2: 8.
Then, identical with embodiment 2, try to achieve 80% the period that the discharge capacity of each battery and discharge capacity are reduced to initial capacity.And 80% the period that the discharge capacity of the battery E1 of embodiment 3 and discharge capacity are reduced to initial capacity is tried to achieve the relative value of battery E6～E10 as 100.Figure 8 shows that the average grain diameter of the alloy powder that active material layer A ' is used and the relation of discharge capacity and cycle characteristics.
We can say that according to Fig. 8 in order to take into account flash-over characteristic and cycle characteristics, the average grain diameter that preferably makes the used alloy powder of active material layer A ' is 5～20 μ m.Average grain diameter for the used alloy powder of active material layer A ' is the battery E6 of 1 μ m and the battery E7 of 5 μ m, because the contact resistance reduction, so flash-over characteristic is good.But,, therefore can think to reach the intensity that increases considerably discharge capacity owing to the ratio of the low very little alloy powder of hydrogen storage capacity increases.In addition, during less than 5 μ m, because the specific area of alloy powder increases, can think that therefore the corrosion of alloy increases in average grain diameter, cycle characteristics reduces.In addition, be the battery E10 of 25 μ m for the average grain diameter of the used alloy powder of active material layer A ', can think the minimizing of counting of alloy and contacting of core can not obtain sufficient flash-over characteristic.
Average grain diameter for the used alloy powder of active material layer A ' is the battery E7 of 5 μ m, is the battery E8 of 10 μ m and is the battery E9 of 20 μ m, takes into account discharge capacity and cycle characteristics well.Thereby, we can say that the average grain diameter of the alloy powder that active material layer A ' is used is preferably 5～20 μ m.
Embodiment 5
The average grain diameter that makes the used alloy powder of active material layer B ' is 15～100 μ m, in addition, makes the battery E11～E17 identical with battery E.Here, the part by weight of the alloy powder that alloy powder that active material layer A ' is contained and active material layer B ' are contained was fixed as 2: 8, and the average grain diameter of the alloy powder that active material layer A ' is used is fixed as 10 μ m.
Then, identical with embodiment 2, try to achieve 80% the period that the discharge capacity of each battery and discharge capacity are reduced to initial capacity.And 80% the period that the discharge capacity of the battery E1 of embodiment 3 and discharge capacity are reduced to initial capacity is tried to achieve the relative value of battery E11～E17 as 100.Figure 9 shows that the average grain diameter of the alloy powder that active material layer B ' is used and the relation of discharge capacity and cycle characteristics.
According to Fig. 9 as can be known, average grain diameter for the alloy powder of active material layer B ' is the battery E11 of 15 μ m and the battery E12 of 20 μ m, because the specific area of alloy is bigger, so flash-over characteristic is good, but because the corrosion of alloy acceleration, so cycle characteristics reduces.In addition we know, be the battery 16 of 75 μ m and the battery 17 of 100 μ m for average grain diameter, because the contact resistance increase between response area minimizing and alloy powder, so flash-over characteristic reduces.
For the average grain diameter of the used alloy powder of active material layer B ' be 25 μ m battery E13, be the battery E14 of 30 μ m and be the battery E15 of 50 μ m, take into account discharge capacity and cycle characteristics well.Thereby, we can say best 25～50 μ m of average grain diameter of the alloy powder that active material layer B ' is used.
Embodiment 6
Battery 1
(1) utilizes the making of the hydrogen-storage alloy powder A1 of atomization
Ratio of components in accordance with regulations weighs commercially available Mm (rare earth alloys), Ni, Mn, Al and Co, in inert gas atmosphere, utilizes high-frequency induction heating dissolving stove to dissolve.The molten alloy that obtains is dripped from the below of crucible, the high pressure argon gas to this molten alloy spraying, is obtained storing the spherical alloy powder A ' of hydrogen.The alloy powder A ' that obtains carries out 1 hour heat treatment in being controlled to 900 ℃ electric furnace.
Alloy powder A ' the composition that obtains is analyzed, and the result is MmNi
3.55Mn
0.4Al
0.3Co
0.75, alloy composition is extremely uniform.In addition, the shape of powder particle is confirmed show it is to show smooth spheroid.
Again above-mentioned alloy powder A ' is screened, particle diameter is become below the 90 μ m, by obtaining the hydrogen-storage alloy powder A1 that average grain diameter is 30 μ m like this.In addition, average grain diameter makes and confirms according to particle size distribution measurement.
(2) utilize the making of the hydrogen-storage alloy powder B1 of comminuting method
Ratio of components in accordance with regulations weighs commercially available Mm (rare earth alloys), Ni, Mn, Al and Co, utilizes high-frequency induction heating dissolving stove to dissolve, and utilizes moulding to make alloy pig.This alloy pig put into is controlled to 1100 ℃ electric furnace, carry out 1 hour heat treatment after, in inert gas, carry out mechanical crushing and obtain hydrogen-storage alloy powder B '.Then above-mentioned alloy powder B ' is screened, make average grain diameter become 15 μ m, obtain having MmNi
3.55Mn
0.4Al
0.3Co
0.75The hydrogen-storage alloy powder B1 of composition.
(3) covering of hydrogen-storage alloy powder B1
After above-mentioned alloy powder B1 being cleaned with acid, put into the mixed liquor that contains the sodium acetate that nickelous sulfate that 30g/ rises and 10g/ rise of heating to 80 ℃, to adding the sodium hypophosphite that 15g/ rises in this solution, carry out stirring in 20 minutes.Then, alloy is washed and drying, obtained the alloy powder B ' that covers with Ni on the surface of alloy powder B1.
Content to the contained nickel of this alloy powder B1 ' is measured, and is confirmed to be 2～5 weight %.
(4) manufacturing of electrode
With the alloy powder B1 ' that obtains of the alloy powder A1 that obtains of 90 weight portions, 10 weight portions, as 0.15 weight portion carboxymethyl cellulose of tackifier, as 0.3 weight portion carbon black of conductive agent, mix, make the alloy paste as 0.8 parts by weight of styrene butadiene copolymer of binding agent and as the water of dispersant.
This paste is coated on the two sides of the iron porous metals that carry out nickel plating of thick 60 μ m, aperture 1mm, percent opening 42%, carries out drying and pressurization.At its surface coverage fluorine resin powder, make the hydrogen-occlussion alloy electrode of wide 35mm, long 150mm, thick 0.4mm, capacity 2200mAh again.
(5) manufacturing of battery
Above-mentioned hydrogen-occlussion alloy electrode and well-known sintered nickel positive electrode across nylon system nonwoven fabrics barrier film, are rolled into helical form, obtain the pole plate group, insert metal shell.Then, that injects ormal weight is dissolved in the electrolyte that the KOH aqueous solution of proportion 1.30 is made with the ratio of 40g/l with lithium hydroxide, and shell is sealed, and makes the enclosed-type battery 1 of 4/5A size, battery capacity 1500mAh.
(1) covering of hydrogen-storage alloy powder A1
After cleaning, be immersed in that to carry out 80 ℃ of proportions of 80 ℃ of having of heating be in 1.30 the KOH aqueous solution, to stir 1 hour with acid identical worth average grain diameter is 30 μ m to (1) of battery 1 alloy powder A1.After this alloy powder washing, put into the mixed liquor that contains the sodium acetate that nickelous sulfate that 30g/ rises and 10g/ rise of heating again to 80 ℃, in the mixed liquor to the sodium acetate of interpolation 15g/ liter in this solution,, carry out stirring in 20 minutes to adding the sodium hypophosphite that 15g/ rises in this solution.
Then, wash and dry, obtain the hydrogen-storage alloy powder A1 ' that the surface to hydrogen-storage alloy powder A1 covers with Ni.
(2) manufacturing of electrode and battery
Use alloy powder A1 ' and the identical alloy powder B1 ' that makes, make the enclosed-type battery 2 identical with battery 1 with (3) of battery 1.
Battery 3
Adopt the method identical to make spherical hydrogen-storage alloy powder A1 with battery 1.
With this hydrogen-storage alloy powder A1 of 100 weight portions, as 0.15 weight portion carboxymethyl cellulose of tackifier, as 0.3 weight portion carbon black of conductive agent, mix, make the alloy paste as 0.8 parts by weight of styrene butadiene copolymer of binding agent and as the water of dispersant.
With this alloy paste, make identical with battery 1 enclosed-type battery 3 of relatively using.
Battery 4
To form average grain diameter be that the hydrogen-storage alloy powder B1 of 15 μ m mixes to the mechanical crushing of carrying out of the hydrogen-storage alloy powder A1 that the employing of 90 weight portions and battery 1 identical method is made and 10 weight portions, obtains alloy powder mixture.
With this mixtures of 100 weight portions, as 0.15 weight portion carboxymethyl cellulose of tackifier, as 0.3 weight portion carbon black of conductive agent, mix, make the alloy paste as 0.8 parts by weight of styrene butadiene copolymer of binding agent and as the water of dispersant.
With this alloy paste, make the enclosed-type battery 4 identical with battery 1.
The evaluation of battery 1～4
(1) flash-over characteristic
With battery under 20 ℃ with current value 1.5A charging, reach theoretical capacity 120% till, again under 0 ℃ with current value 3.0A discharge, cell voltage is reduced till the 1.0V, measure discharge capacity (initial discharge capacity) at this moment.
The initial discharge capacity of battery 3 as 100, is represented the initial discharge capacity of each battery with relative value.The results are shown in the table 3, so long as more than 110, it is passable that flash-over characteristic can be thought.
(2) cycle characteristics
With battery under 20 ℃ with current value 1.5A charging, reach theoretical capacity 120% till, with current value 1.5A discharge, reach till the cell voltage 1.0V again, repeat above-mentioned such circulation.Then, try to achieve 80% the period that discharge capacity is reduced to initial discharge capacity.The period of battery 3 as 100, is represented the period of each battery with relative value.Show the result in the table 3.Cycle characteristics can be thought and is necessary for more than 90.
Table 3
| Battery | Alloy powder | Discharge capacity | Cycle characteristics |
| 1 | Alloy powder A1 Ni lining alloy powder B1 ' | 117 | 94 |
| 2 | Ni lining alloy powder A1 ' Ni lining alloy powder B1 ' | 115 | 97 |
| 3 | | 100 | 100 |
| 4 | Alloy powder A1 alloy powder B1 | 83 |
According to the result of battery 1～4 as can be known, pulverize the alloy powder B1 that obtains by having mixed to utilize, flash-over characteristic improves.This can think because, utilize the alloy powder that obtains of mechanical crushing by use, the reaction table area increases, and then has improved the contact condition between core and the alloy powder.
The result that battery 1 and battery 4 arranged covers with Ni by the alloy surface to mechanical crushing as can be known, can guarantee sufficient cycle characteristics.In addition, according to the result of battery 1 and battery 2 as can be known, by the alloy powder surface that utilizes atomization to obtain is covered with Ni, cycle characteristics can further improve.This can think because, cover with Ni by surface spherical alloy powder, can further suppress the corrosion reaction of alloy.
Embodiment 7
In the present embodiment, be of the influence of the particle diameter of the spherical hydrogen-storage alloy powder A that obtains of research and utilization atomization to battery behavior.As the pulverizing alloy powder B that mixes with spherical alloy powder A, be to use by the sieve classification of 20 μ m and the alloy powder that covers with Ni on its surface.In addition, spherical alloy powder A is 90: 10 with the weight mixing ratio of pulverizing alloy powder B.
The identical spherical alloy powder A ' classification that utilizes sieve to obtain with embodiment 6, obtaining average grain diameter respectively is spherical alloy powder A2, A3, A4, A5, A6 and the A7 of 15,20,30,40,45 and 65 μ m.Except adopting alloy powder A2, A3, A4, A5, A6 and A7.Except adopting alloy powder A2, A3, A4, A5, A6 and A7, all the other are identical with embodiment 6, make enclosed-type battery 5～10 respectively.Identical with enforcement 6, make enclosed-type battery 5～10 respectively.With implement 6 identically, try to achieve the flash-over characteristic and the cycle characteristics of resulting battery, represent with relative value.Show the result in the table 4.
Table 4
| Battery | The size (μ m) of sieve | The average grain diameter of alloy powder A (μ m) | Discharge capacity | Cycle characteristics |
| 5 | 40 | 15 | 122 | 86 |
| 6 | 40 | 20 | 120 | 90 |
| 7 | 75 | 30 | 117 | 94 |
| 8 | 75 | 40 | 112 | 96 |
| 9 | 90 | 45 | 109 | 97 |
| 10 | 100 | 65 | 108 | 89 |
According to table 4 as can be known, the average grain diameter along with hydrogen-storage alloy powder A reduces the flash-over characteristic raising of the battery that obtains, otherwise cycle characteristics reduction.For adopting with average grain diameter is the battery 5 of the alloy powder A2 of 15 μ m, and cycle characteristics is insufficient.This be because, if particle diameter reduces, then the specific area of alloy powder increases, flash-over characteristic improves, otherwise and the surface area that is corroded increases, cycle characteristics reduces.
In addition, be the battery 10 of the alloy powder A7 of 65 μ m for adopting average grain diameter by the sieve classification of 100 μ m, because response area reduces, the discharge capacity at the initial stage of therefore circulating reduces.
Result according to table 4 we can say that spherical alloy powder A preferably has following particle diameter of 90 μ m and the average grain diameter of 20～40 μ m.
Embodiment 8
In the present embodiment, be that research and utilization is pulverized the influence of the particle diameter of the hydrogen-storage alloy powder B that obtains to battery behavior.As the hydrogen-storage alloy powder A that utilizes atomization to make, being to use the average grain diameter by the sieve classification of 90 μ m is the alloy powder of 30 μ m.In addition, spherical alloy powder A is 90: 10 with the weight mixing ratio of pulverizing alloy powder B.
The identical hydrogen-storage alloy powder B ' classification that utilizes sieve to obtain with embodiment 6, obtaining average grain diameter respectively is pulverizing alloy powder B2, B3, B4, B5 and the B6 of 7,10,12,15 and 20 μ m.Except adopting the pulverizing alloy powder of surface with the Ni covering that will pulverize alloy powder B2, B3, B4, B5 and B6, all the other are identical with battery 1, make enclosed-type battery 11～15 respectively.Identical with embodiment 6, try to achieve the flash-over characteristic and the cycle characteristics of resulting battery, represent with relative value.Show the result in the table 5.
Table 5
| Battery | Average grain diameter (μ m) | Discharge capacity | Cycle characteristics |
| 11 | 7 | 117 | 83 |
| 12 | 10 | 118 | 90 |
| 13 | 12 | 118 | 91 |
| 14 | 15 | 117 | 94 |
| 15 | 20 | 114 | 89 |
According to table 5 as can be known, when the average grain diameter of pulverizing alloy powder B is 10～15 μ m, can access good flash-over characteristic, cycle characteristics is also fine.But, be reduced to the battery 11 about 7 μ m and increase to battery 15 about 20 μ m for the average grain diameter that will pulverize alloy powder B, though can access good flash-over characteristic, cycle characteristics reduces.For battery 11, can think because the specific area of alloy powder B increases, thereby the alkaline electrolyte seriously corroded.For battery 15, think big alloy powder B as can be known owing to charge and discharge cycles produces micronizing, the seriously corroded that the alloy surface that does not cover Ni of new generation is produced.According to these situations as can be known, the average grain diameter of pulverizing alloy powder B is preferably 10～15 μ m.
In the present embodiment, be the spherical hydrogen-storage alloy powder A and the influence of the weight ratio of pulverizing hydrogen-storage alloy powder B to battery behavior in the research hydrogen-occlussion alloy electrode, spherical alloy powder A is 95: 5,90: 10,80: 20 or 75: 25 with the weight ratio of pulverizing alloy powder B.
As spherical alloy powder A, being to use the average grain diameter with the sieve classification of 90 μ m is the alloy powder of 30 μ m; As pulverizing alloy powder B, being to use average grain diameter with the sieve classification of 20 μ m is 15 μ m and alloy powder that alloy surface is covered with Ni.In addition, identical with battery 1, make enclosed-type battery 16～19.Identical with embodiment 6, try to achieve the flash-over characteristic and the cycle characteristics of resulting battery, represent with relative value.Show the result in the table 6.
Table 6
| Battery | The weight mixing ratio | Discharge capacity | Cycle characteristics |
| Alloy powder A: alloy powder B: | |||
| 16 | 95∶5 | 112 | 96 |
| 17 | 90∶10 | 117 | 94 |
| 18 | 80∶20 | 120 | 91 |
| 19 | 75∶25 | 116 | 89 |
According to table 6 as can be known, when making the ratio of pulverizing alloy powder B in whole alloys be 5～20 weight %, can access good flash-over characteristic, cycle characteristics is also fine.In addition, when the ratio of pulverizing alloy powder B was 25 weight %, though flash-over characteristic is good, cycle characteristics was insufficient.This can think because, increase if pulverize the mixed proportion of alloy powder B, then along with charge and discharge cycles, the seriously corroded of alloy consumes electrolyte.We can say according to these situations, pulverize the ratio of alloy powder B in whole hydrogen-storage alloy powders and be preferably 5～20 weight %.
In addition, in the above-described embodiments, be to utilize non-electrolysis to cover with nickel, but be not limited to this pulverizing alloy powder.Adopting electrolysis and with the caustic solution of acid or alkaline solution etc., is nickel and cobalt covering powder surface with the formation element of storage hydrogen total, also can access same effect.
The possibility of utilizing on the industry
Among the present invention, owing to adopt the spherical hydrogen-storage alloy powder that is difficult to micronizing and is difficult to be subjected to the alkaline electrolysis corrosion, and the modified electrode core contacts with alloy powder, and therefore all alkaline storage batteries of excellence of flash-over characteristic and cycle characteristics two aspects can be provided.
Claims (6)
1. hydrogen-occlussion alloy electrode by the conductivity core and utilize the active material layer that contains hydrogen-storage alloy powder of described core support to constitute, is characterized in that,
Any shape that described alloy powder has is spherical, select in the approximate spherical and egg-shape,
Described core has in the longitudinal direction at interval and forms many, and above-below direction is the mesh sheets of the slit of approximate diamond opening.
2. an alkaline battery is made of positive pole, negative pole, barrier film and alkaline electrolyte, it is characterized in that, described negative pole is the described hydrogen-occlussion alloy electrode of claim 1.
3. the autofrettage of a hydrogen-occlussion alloy electrode is characterized in that, has step as described below, promptly
Step (a) is provided with the coupling part shorter than slit at interval for many slits on the conductive sheet on the length direction of described sheet material, form staggered shape;
Step (b) is on the Width of described slit, and the part that adjacent slots is clipped alternately encircles up and down, make described slit up and down direction be approximate diamond opening, by obtaining the core of mesh sheets like this; And
Step (c) manufacturing has the hydrogen-storage alloy powder of any shape of selecting in spherical, approximate spherical and the egg-shape, and modulation contains the paste of this powder, and this paste is attached on the described core.
4. the autofrettage of hydrogen-occlussion alloy electrode as claimed in claim 3 is characterized in that,
Described step (c) comprises following step (c-1), step (c-2), step (c-3),
Described step (c-1) is utilized atomization or centrifugal spray method, make the hydrogen-storage alloy powder A of the average grain diameter a with any shape of selecting in spherical, approximate spherical and the egg-shape respectively and have spherical, as to be similar to the average grain diameter b of any shape of selecting in spherical and egg-shape hydrogen-storage alloy powder B, here, a＜b;
Described step (c-2) modulation contains the paste A of described alloy powder A, and paste A is attached on the described core;
Described step (c-3) modulation contains the paste B of described alloy powder B, coating paste B on described paste A.
5. the autofrettage of hydrogen-occlussion alloy electrode as claimed in claim 4 is characterized in that,
Described step (c-1) is such step, promptly makes the hydrogen-storage alloy powder with particle size distribution, with the alloy powder screening that the obtains described alloy powder B for the described alloy powder A of average grain diameter a and average grain diameter b.
6. the autofrettage of hydrogen-occlussion alloy electrode as claimed in claim 3 is characterized in that,
Described step (c) comprises step (C-4), step (c-5), step (c-6) and step (c-7), promptly
The hydrogen-storage alloy powder C of any shape of selecting in spherical, the approximate spherical and egg-shape that described step (c-4) is utilized atomization or centrifugal spray method to make to have;
Described step (c-5) utilizes mechanical crushing method to make shaggy hydrogen-storage alloy powder D;
Described step (c-6) makes at least a material of selecting in the surface attachment nickel of described alloy powder D and the cobalt;
Described step (c-7) modulation contains described alloy powder C and surperficial paste with described alloy powder D of at least a material of selecting in nickel and the cobalt, and described paste is invested on the described core.
Applications Claiming Priority (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000250648A JP2002063896A (en) | 2000-08-22 | 2000-08-22 | Hydrogen storage alloy electrode and alkaline battery using the same |
| JP250648/00 | 2000-08-22 | ||
| JP250648/2000 | 2000-08-22 | ||
| JP008498/2001 | 2001-01-17 | ||
| JP2001008498A JP3951609B2 (en) | 2001-01-17 | 2001-01-17 | Air conditioner installation equipment |
| JP008496/01 | 2001-01-17 | ||
| JP2001037624A JP4932997B2 (en) | 2001-02-14 | 2001-02-14 | Hydrogen storage alloy electrode and alkaline storage battery using the same |
| JP037624/01 | 2001-02-14 | ||
| JP037624/2001 | 2001-02-24 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1465110A CN1465110A (en) | 2003-12-31 |
| CN1260837C true CN1260837C (en) | 2006-06-21 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB018145272A Expired - Fee Related CN1260837C (en) | 2000-08-22 | 2001-08-10 | Alkali storage battery and hydrogen absorbing alloy electrode for use therein |
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| Country | Link |
|---|---|
| CN (1) | CN1260837C (en) |
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2001
- 2001-08-10 CN CNB018145272A patent/CN1260837C/en not_active Expired - Fee Related
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| Publication number | Publication date |
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| CN1465110A (en) | 2003-12-31 |
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| CI01 | Correction of invention patent gazette |
Correction item: [31] (second) Correct: 008496/2001 False: 008498/2001 Number: 53 Page: 322 Volume: 19 Correction item: [32] (third) Correct: 20010214 False: 20010224 Number: 53 Page: 322 Volume: 19 |
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| CI02 | Correction of invention patent application |
Correction item: [31] (second) Correct: 008496/2001 False: 008498/2001 Number: 53 Page: The title page Volume: 19 Correction item: [32] (third) Correct: 20010214 False: 20010224 Number: 53 Page: The title page Volume: 19 |
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| COR | Change of bibliographic data |
Free format text: CORRECT: ¢31! (NO.2 ) ¢32! (NO.3 ); FROM: 008498/2001 2001.2.24 TO: 008496/2001 2001.2.14 |
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| ERR | Gazette correction |
Free format text: CORRECT: ¢31! (NO.2 ) ¢32! (NO.3 ); FROM: 008498/2001 2001.2.24 TO: 008496/2001 2001.2.14 |
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| CF01 | Termination of patent right due to non-payment of annual fee |